Golf balls incorporating HNP ionomers based on highly diverse mixtures of organic acids

ABSTRACT

Golf ball incorporating an HNP composition consisting of a mixture of: at least one ethylene acid copolymer; sufficient amount of cation source to neutralize greater than about 100% of all acid groups present; and a highly diverse mixture of at least four organic acids having different characteristics such as relating to: carbon chain lengths, number of double bonds on carbon chains, positioning of double bonds on carbon chains, number of branches, types of branches, positioning of branches on carbon chains, positioning of acid groups on carbon chains, configurations (cis/trans), functional groups on carbon chains, being saturated/unsaturated, being conjugated/non-conjugated; presence/absence of functional group(s) on carbon chain; being aliphatic/aromatic, or combinations thereof. No organic acid is present in highly diverse mixture in a concentration greater than 80%, or, in some embodiments, greater than 60%, or greater than 40%. HNP composition may be relatively soft/relatively low modulus, relatively hard/relatively high modulus, or blends thereof.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 14/145,593 (“'593 appl.”), filed Dec. 31, 2013, now U.S. Pat.No. 9,427,630, which is a continuation-in-part of U.S. patentapplication Ser. No. 13/692,583, filed Dec. 3, 2012, now U.S. Pat. No.8,740,726, which is a continuation of U.S. patent application Ser. No.13/169,753, filed Jun. 27, 2011, now U.S. Pat. No. 8,323,123, which is acontinuation of U.S. patent application Ser. No. 12/795,295, filed Jun.7, 2010, now U.S. Pat. No. 7,967,701, which is a continuation of U.S.patent application Ser. No. 12/125,306, filed May 22, 2008, now U.S.Pat. No. 7,731,607, which is a continuation-in-part of U.S. patentapplication Ser. No. 11/972,240, filed Jan. 10, 2008, now U.S. Pat. No.7,722,482, and U.S. patent application Ser. No. 11/738,759, filed Apr.23, 2007, now U.S. Pat. No. 7,517,289, which is a continuation-in-partof U.S. patent application Ser. No. 11/304,863, filed Dec. 15, 2005, nowU.S. Pat. No. 7,211,008, the entire disclosures of which are herebyincorporated herein by reference.

The '593 appl. is also a continuation-in-part of U.S. patent applicationSer. No. 13/758,041, filed Feb. 4, 2013, now U.S. Pat. No. 8,740,724,which is a continuation of U.S. patent application Ser. No. 13/329,398,now U.S. Pat. No. 8,382,611, which is a continuation of U.S. patentapplication Ser. No. 12/697,368, filed Feb. 1, 2010, now U.S. Pat. No.8,079,920, which is a continuation of U.S. patent application Ser. No.12/125,260, filed May 22, 2008, now U.S. Pat. No. 7,654,916. U.S. patentapplication Ser. No. 12/125,260 is a continuation-in-part of U.S. patentapplication Ser. No. 11/694,007, filed Mar. 30, 2007, now U.S. Pat. No.7,452,290, which is a continuation of U.S. patent application Ser. No.11/304,962, filed Dec. 15, 2005, now U.S. Pat. No. 7,207,903. U.S.patent application Ser. No. 12/125,260 is also a continuation-in-part ofU.S. patent application Ser. No. 12/048,003, filed Mar. 13, 2008, nowabandoned. U.S. patent application Ser. No. 12/125,260 is also acontinuation-in-part of U.S. patent application Ser. No. 12/048,021,filed Mar. 13, 2008, now U.S. Pat. No. 8,357,059. The entire disclosureof each of these references is hereby incorporated herein by reference.

The '593 appl. application is also a continuation-in-part of Ser. No.13/584,167, filed Aug. 13, 2012, now U.S. Pat. No. 8,702,536, which is acontinuation of U.S. patent application Ser. No. 13/164,233, filed Jun.20, 2011, now U.S. Pat. No. 8,241,147, which is a continuation of U.S.patent application Ser. No. 12/125,320, filed May 22, 2008, now U.S.Pat. No. 7,963,862, which is a continuation-in-part of U.S. patentapplication Ser. No. 11/738,759, filed Apr. 23, 2007, now U.S. Pat. No.7,517,289, which is a continuation-in-part of U.S. patent applicationSer. No. 11/304,863, filed Dec. 15, 2005, now U.S. Pat. No. 7,211,008,the entire disclosures of which are hereby incorporated herein byreference. U.S. patent application Ser. No. 12/125,320 is also acontinuation-in-part of U.S. patent application Ser. No. 11/972,259,filed Jan. 10, 2008, now U.S. Pat. No. 7,753,810, the entire disclosureof which is hereby incorporated herein by reference.

FIELD OF THE INVENTION

The present invention is directed to golf balls incorporating at leastone golf ball layer such as a core, intermediate layer, cover layerand/or coating layer comprising a highly neutralized acid polymer (HNP)composition or blends thereof.

BACKGROUND OF THE INVENTION

Conventional golf balls can be divided into two general classes: solidand wound. Solid golf balls include one-piece, two-piece (i.e., singlelayer core and single layer cover), and multi-layer (i.e., solid core ofone or more layers and/or a cover of one or more layers) golf balls.Wound golf balls typically include a solid, hollow, or fluid-filledcenter, surrounded by a tensioned elastomeric material, and a cover.

Golf ball core and cover layers are typically constructed with polymercompositions including, for example, polybutadiene rubber,polyurethanes, polyamides, ionomers, and blends thereof. Playingcharacteristics of golf balls, such as spin, feel, CoR and compressioncan be tailored by varying the properties of the golf ball materialsand/or adding additional golf ball layers such as at least oneintermediate layer disposed between the cover and the core. Intermediatelayers can be of solid construction, and have also been formed of atensioned elastomeric winding. The difference in play characteristicsresulting from these different types of constructions can be quitesignificant.

Ionomers, particularly ethylene-based ionomers, are a preferred group ofpolymers for golf ball layers because of their toughness, durability,and wide range of hardness values. Ionomers initially became populargolf ball cover materials due to their excellent impact resistance andtheir thermaplasticity, which permits the material to be economicallyapplied via injection or compression molding techniques.

Specifically, highly neutralized acid polymers or HNPs, are beneficial.For example, U.S. Patent Application Publication No. 2003/0130434, theentire disclosure of which is hereby incorporated herein by reference,discloses melt-processible, highly-neutralized ethylene acid copolymersand processes for making them by incorporating an aliphatic,mono-functional organic acid in the acid copolymer and then neutralizinggreater than 90% of all the acid groups present. Also, in U.S. PatentApplication Publication No. 2005/0148725, the entire disclosure of whichis hereby incorporated herein by reference, highly-resilientthermoplastic compositions comprising (a) an acid copolymer, (b) a saltof an organic acid; (c) a thermoplastic resin; (d) a cation source; and(e) optionally, a filler are disclosed. The reference also disclosesone-piece, two-piece, three-piece, and multi-layered golf ballscomprising such highly-resilient thermoplastic compositions.

However, there is a need in the golf ball industry to develop and refinehighly neutralized acid polymer materials that display excellentresilience at given compressions and with soft feel. Golf balls of thepresent invention and the methods of making same address and solve thisneed.

SUMMARY OF THE INVENTION

Accordingly, golf balls of the invention comprise at least one layercomprising an HNP composition consisting of a mixture of: at least oneethylene acid copolymer; a sufficient amount of cation source toneutralize greater than about 100% of all acid groups present; and ahighly diverse mixture of organic acids. As used herein, the term“highly diverse mixture of organic acids” refers to a mixture of atleast four organic acids with at least one different characteristic suchas: (i) having different carbon chain lengths; or (ii) being saturatedand unsaturated; or (iii) having a different number of double bonds onthe carbon chains; or (iv) having double bonds positioned differently onthe carbon chains; or (v) having a different number of branches on thecarbon chains; or (vi) having different types of branches on the carbonchains; or (vii) having branches positioned differently on the carbonchains; or (viii) having acid groups positioned differently on thecarbon chains; or (ix) having different carbon-carbon double bondconfigurations (cis/trans); or (x) being conjugated and non-conjugated;or (xi) having presence and absence of functional group(s) on the carbonchains; or (xii) having different functional groups on the carbonchains; or (xiii) being aliphatic and aromatic; or (xiv) combinationsthereof.

In one embodiment, the highly diverse mixture contains greater than fourorganic acids. In yet another embodiment, the highly diverse mixturecontains greater than six organic acids. In still another embodiment,the highly diverse mixture contains greater than ten organic acids.Alternatively, the highly diverse mixture may contain greater thanfifteen organic acids.

In one embodiment, all organic acids are carboxylic acids. In someembodiments, at least 90% of the organic acids of the highly diversemixture are fatty acids.

In one embodiment, at least two organic acids of the highly diversemixture have different carbon chain lengths. For example, the carbonchain lengths may differ by at least two carbon atoms. In anotherembodiment, at least three organic acids of the highly diverse mixturehave different carbon chain lengths. For example, the carbon chainlengths may differ by at least two carbons.

In one embodiment, no single organic acid is present in the highlydiverse mixture in a concentration greater than 80%. In anotherembodiment, no single organic acid is present in the highly diversemixture in a concentration greater than 60%. In yet another embodiment,no single organic acid is present in the highly diverse mixture in aconcentration greater than 40%.

The highly diverse mixture may contain saturated organic acids andunsaturated organic acids. In one embodiment, one organic acid may havea carbon chain having a different number of carbon-carbon double bondsthan a carbon chain of at least one other organic acid. Additionally oralternatively, a first organic acid may have a first carbon chain, and asecond organic acid may have a second carbon chain having the samenumber of carbon-carbon double bonds as the first carbon chain; andwherein at least one carbon-carbon double bond position on the firstcarbon chain is not a carbon-carbon double bond position on the secondcarbon chain.

Further, at least one organic acid may have a cis-type carbon-carbondouble bond configuration while at least one other organic acid has atrans-type carbon-carbon double bond configuration.

Additionally or alternatively, at least one organic acid may have acarbon chain that is branched differently than a carbon chain of atleast one other organic acid. For example, one organic acid may have acarbon chain having a different number of branches than a carbon chainof at least one other organic acid.

Moreover, a first organic acid may have a first carbon chain, and asecond organic acid may have a second carbon chain having the samenumber of branches as the first carbon chain; and wherein at least onebranch position on the first carbon chain is not a branch position onthe second carbon chain.

In one embodiment, at least two organic acids may have differentfunctional groups. One functional group, for example, may be carboxylicacid. Additionally or alternatively, the highly diverse mixture maycomprise at least one aliphatic organic acid and at least one aromaticorganic acid.

In one embodiment, the highly diverse mixture may contain organic acidshaving two or more different characteristics. In another embodiment, thehighly diverse mixture may contain organic acids having three or moredifferent characteristics. In yet another embodiment, the highly diversemixture may contain organic acids having four or more differentcharacteristics. In still another embodiment, the highly diverse mixturecontains organic acids having five or more different characteristics.

The invention also relates to the HNP composition consisting of amixture of: at least one ethylene acid copolymer; a sufficient amount ofcation source to neutralize greater than about 100% of all acid groupspresent; and a highly diverse mixture of organic acids. The HNPcomposition can be relatively soft (or relatively low modulus), orrelatively hard (or relatively high modulus), or a blend thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings form a part of the specification and are to beread in conjunction therewith. The illustrated embodiments, however, aremerely examples and are not intended to be limiting. In each figure,numerals are used to count some of the organic acids as well as to ordersame according to decreasing chromatographic peak area, and therefore,like reference numerals appearing in the various drawings do notnecessarily indicate like organic acids.

FIG. 1 is a chromatogram of one highly diverse mixture of organic acids;

FIG. 2 is a chromatogram of another highly diverse mixture of organicacids; and

FIG. 3 is a chromatogram of yet another highly diverse mixture oforganic acids.

DETAILED DESCRIPTION OF THE INVENTION

Golf balls of the present invention have at least one layer thatcomprises a highly neutralized acid polymer (“HNP”) compositionconsisting of a mixture of at least one ethylene acid copolymer; asufficient amount of cation source to neutralize greater than about 100%of all acid groups present; and a highly diverse mixture of organicacids. The resulting HNP composition has excellent resilience at a givencompression and can have soft feel at a given CoR and meanwhileproviding increased design flexibility with controlled manufacturingcosts.

As used herein, the term “highly neutralized acid polymer” or HNP refersto an acid polymer after at least 80%, preferably at least 90%, morepreferably at least 95%, and even more preferably 100%, of all acidgroups present are neutralized. However, the cation source may presentin an amount sufficient to neutralize, theoretically, greater than 100%,or 105% or greater, or 110% or greater, or 115% or greater, or 120% orgreater, or 125% or greater, or 200% or greater, or 250% or greater ofall acid groups present in the composition. The cation source may beprovided in an amount sufficient to neutralize, in a stoichiometricsense, greater than 100% of the acid groups, because the neutralizationprocess is less than perfectly efficient.

As used herein, the term “copolymer” refers to a polymer which is formedfrom two or more monomers. The ethylene acid copolymer can be mixed withthe highly diverse mixture of organic acids and the cation sourcesimultaneously, or the ethylene acid copolymer can be mixed with thehighly diverse mixture of organic acids prior to addition of the cationsource. Examples of suitable ethylene acid copolymers, such as ethyleneterpolymers, are set forth further below.

The term “organic acid”, as used herein, refers to an organic compoundcontaining an acid functional group, such as, but not limited to acarboxylic acid, sulfonic acid, or phosphonic/phosphinic acid functionalgroup. The compound may contain additional functional groups includingone or more additional acid functional group. Thus, the highly diversemixture may include non-fatty acids containing the carboxyl radical—COOH as well as fatty acids.

A diverse mixture of organic acids incorporates at least four organicacids with different characteristics such as having different carbonchain lengths; being saturated and unsaturated; having a differentnumber of double bonds on the carbon chains; having double bondspositioned differently on the carbon chains; having a different numberof branches on the carbon chains; having different types of branches onthe carbon chains; having branches positioned differently on the carbonchains; having acid groups positioned differently on the carbon chains;having different carbon-carbon double bond configurations (cis/trans);being conjugated and non-conjugated; having presence and absence offunctional group(s) on the carbon chains; having different functionalgroups on the carbon chains; being aliphatic and aromatic; orcombinations thereof.

In this regard, the term “carbon chain”, as used herein, refers to achain of connected atoms comprised primarily of carbon. The chain may belinear, cyclic or polycyclic.

In other embodiments, the highly diverse mixture of organic acids maycomprise greater than four organic acids; or at least six organic acids;or greater than six organic acids; or at least nine organic acids; orgreater than nine organic acids; or at least fifteen organic acids; orgreater than fifteen organic acids; or at least nineteen organic acids;or greater than nineteen organic acids; or at least twenty five organicacids; or greater than twenty five organic acids; or at least thirtyorganic acids; or greater than thirty organic acids; or at least fortyorganic acids; or even greater than forty organic acids.

In yet other embodiments, the highly diverse mixture of organic acidsmay comprise from four to about six organic acids; or from four to aboutnine organic acids; or from six to about nine organic acids; or from sixto about twelve organic acids; or from nine to about twelve organicacids; or from nine to about nineteen organic acids; or from twelve toabout nineteen organic acids; or from nineteen to about forty fiveorganic acids; or from thirty to about forty five organic acids.

In still other embodiments, the highly diverse mixture of organic acidsmay comprise from about six to about twelve organic acids; or from aboutnine to about twelve organic acids; or from about nine to about nineteenorganic acids; or from about twelve to about nineteen organic acids; orfrom about nineteen to about forty five organic acids; or from aboutthirty to forty five organic acids. However, embodiments are indeedenvisioned wherein the highly diverse mixture of organic acids comprisesgreater than forty five organic acids.

Without being bound to any particular theory, it is believed that ahighly diverse mixture of organic acids, consisting of molecules havingdifferent sizes and shapes, results in an overall lowering of the totalcrystallinity of the system. In particular, the ability of both theorganic acids (which can make up 40% or more of the weight of thepolymer) and polymer to crystallize is reduced. Such reducedcrystallinity of the polymer system and increased amorphous content(lacking long-range order or geometrical shape) improves CoR at a givencompression and/or improves feel at a given CoR, as well as creates longterm property stability (e.g., compression, hardness, CoR) and impactdurability. Property creep, known to result from a polymercrystallizing, can be reduced.

In contrast, more ‘pure’ fatty acids, being substantially generally ofthe same shape and conformation, can undesirably ‘stack’ more easily toform crystalline regions in the polymer, therefore producing a structurethat is very defined and carries a distinct pattern. Because of thisuniformity, disruption of the polymer crystallinity is less efficient.

Organic acids of a highly diverse mixture can be separated and displayedas depicted in the chromatograms of FIG. 1, FIG. 2 and FIG. 3 using agas chromatograph/mass spectrometer (“GC/MS”) such as Thermo Scientific™Ultra TRACE GC Ultra Gas Chromatograph with a DSQ II Mass SpectrometerDetector (“DSQ II”). The GC part of the DSQ II can separate all of thecomponents in a sample and provide a spectral output with a spectralpeak located at each component's retention time—that is, the timeelapsed between when the sample is injected into the device and wheneach particular analyte elutes from the GC column in the DSQ II.

Organic acids having different retention times necessarily differ. Whilethe GC component of the device is effective in separating the organicacids, the MS component of the device can effectively display eachorganic acid/fatty acid derivative in the form of mass spectral data.Accordingly, the chromatograms of FIG. 1, FIG. 2 and FIG. 3 wereproduced by injecting methylated forms of one of Century® D1(commercially available from Arizona Chemical Co., Inc.), Sylfat® FA2(commercially available from Arizona Chemical Co., Inc.), and Sylfat®2LT respectively, in into the DSQ II for analysis. In each of FIG. 1,FIG. 2 and FIG. 3, every organic acid has a different retention timealong the “Time” axis as well as a unique distinct spectral peak.

In FIG. 1 (Century® D1), twenty organic acids are labelled/numbered inorder of decreasing chromatographic peak area. In turn, in FIG. 2(Sylfat® FA2) and FIG. 3 (Sylfat® 2LT), fourteen and fifteen organicacids are so labelled/numbered, respectively. At least one of thesediverse mixtures was used to make the HNP spheres of examples Ex. 1 andEx. 2, Ex. 3, Ex. 4, Ex. 5, and Ex. 6 of TABLE 1 and TABLE 2 hereinbelow.

In this regard, six inventive HNP spheres Ex. 1, Ex. 2, Ex. 3, Ex. 4,Ex. 5, and Ex. 6 were formed and compared with four comparative spheresComp-Ex. 1, Comp-Ex. 2, Comp-Ex. 3 and Comp-Ex. 4. The exactformulations for inventive spheres Ex. 1, Ex. 2, Ex. 3, Ex. 4, Ex. 5,Ex. 6 and comparative spheres Comp-Ex. 1, Comp-Ex. 2, Comp-Ex. 3 andComp-Ex. 4 are set forth in TABLE 1 as follows:

TABLE 1 SOLID SPHERE FORMULATIONS (%) Comp- Comp- Comp- Comp-INGREDIENTS Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 1 Ex. 2 Ex. 3 Ex. 4Escor AT320¹ 60 60 60 60 60 60 61 60 60 60 Century D1FA² 40 40 8 SylfatFA2³ 40 40 8 Oleic Acid 8 39 40 Sylfat 2LT⁴ 40 8 Behenic Acid 8 40Erucic Acid 40 ¹Escor ® AT320 is an ethylene/acrylic acid/methylacrylate polymer, commercially available from ExxonMobil ChemicalCompany; ²Century ® D1FA is a mixture of branched and straight chainfatty acids, commercially available from Arizona Chemical Co., Inc.³Sylfat ® FA2 is a tall oil fatty acid (TOFA) having a partiallyunsaturated C18 backbone, commercially available from Arizona ChemicalCo., Inc. ⁴Sylfat ® 2LT is a TOFA with a high fatty acid content and alow content of rosin acids, commercially available from Arizona ChemicalCo., Inc.

The ingredients for each sphere identified in Table 1 were melt blended.Each of the 10 spheres included the same ethylene/acrylic acid/methylacrylate polymer set forth in Table 1, and magnesium hydroxide was usedas the cation source, added in an amount sufficient to neutralize,theoretically, 105 or 125% of the acid groups present. Inventive spheresEx. 1, Ex. 2, Ex. 3, Ex. 4, Ex. 5, and Ex. 6 were made using one of thediverse organic acid mixtures identified in TABLE 1, whereas each ofcomparative spheres Comp-Ex. 1, Comp-Ex. 2, Comp-Ex. 3 and Comp-Ex. 4incorporated oleic, behenic, or erucic acid.

Solid 1.550″ spheres of each composition were injection molded, and theCoR, compression, Shore D hardness, and Shore C hardness of theresulting solid spheres were measured after two weeks. The results arereported in TABLE 2 as follows:

TABLE 2 EXAMPLES Comp- Comp- Comp- Comp- PROPERTY Ex. 1 Ex. 2 Ex. 3 Ex.4 Ex. 5 Ex. 6 Ex. 1 Ex. 2 Ex. 3 Ex. 4 % Neutral. 105 125 105 125 105 105105 125 105 105 Mg(OH)₂ CoR 0.806 0.816 0.835 0.813 0.803 0.822 0.7830.798 0.761 0.803 Comp. 76 75 76 71 68 85 69 75 126 66 (DCM) Hardness45.6 48.3 46.3 42.2 41.3 47.6 40.3 43.2 57.7 45.9 (Shore D) Hardness71.9 76.3 68.2 69.8 68.2 77.6 66.2 70.3 89.4 72.1 (Shore C)

As is shown in TABLE 2, each of inventive spheres Ex. 1, Ex. 2, Ex. 3,Ex. 4, Ex. 5, Ex. 6, incorporating a highly diverse mixture of fattyacids, has a CoR that is greater than the CoRs of comparative spheresComp-Ex. 1, Comp-Ex. 2, and Comp-Ex. 3. Meanwhile, inventive sphere Ex.5 and comparative sphere Comp-Ex. 4 have a similar CoR of 0.803 butnoticeably differ in that sphere Ex. 5 has a hardness that is 4.9 ShoreC hardness points and 4.6 Shore D hardness points lower than comparativesphere Comp-Ex. 4, which can impart a softer feel to inventive sphereEx. 5 as compared with comparative sphere Comp-Ex. 4.

Thus, golf balls of the invention incorporating an HNP composition asdisclosed herein have desirable properties such as excellent CoR at agiven compression compared with HNPs formed from more pure organicacids.

Organic acids having different carbon chain lengths have differentgeneral structural formulas. For example, one organic acid may have analiphatic chain/tail having 16 carbons (C16), whereas another organicacid of the highly diverse mixture has an aliphatic chain/tail having 17carbons (C17). Further, organic acids can have carbon chain lengths thatdiffer to such an extent that the organic acids are classifieddifferently within the categories of “short chain”, “medium chain”,“long chain”, or “very long chain”. In this regard, the term “shortchain” refers to organic acids with carbon chains/tails of less than 6carbons; the term “medium chain” refers to organic acids with carbonchains/tails of 6-12 carbons; the term “long chain” refers to organicacids with carbon chains/tails of 13-21 carbons; and the term “very longchain” refers to organic acids with carbon chains/tails longer than 22carbons. Thus, embodiments are envisioned wherein a highly diversemixture includes organic acids from two or more of theseclassifications, or any or all of these classifications.

Two organic acids may share the same general formula, such as C18:1, yethave other distinguishing characteristics such as those disclosedherein. (In the structural formula C18:1, “18” represents the number ofcarbons on the carbon chain of the organic acid, and “1” represents thenumber of double bonds in the carbon chain). For example, a diversemixture of organic acids may have four organic acids wherein each of theorganic acids has one of the general structural formulas 16:1; 18:0; and18:1, with 50% of the organic acids sharing the general formula 18:1being branched. (In a branched organic acid, the parent hydrocarbonchain has one or more alkyl substituents). While methyl is the mostcommon branching group, other branching groups such as ethyl, propyl,butyl, etc., are known and contemplated as embodiments. Individualorganic acids of a highly diverse mixture can be specifically identifiedvia derivation methods such as in “Fatty Acid/FAME Application Guide”,by Sigma-Aldrich, hereby incorporated by reference herein in itsentirety.

In another example, a highly diverse mixture of organic acids mayincorporate at least five organic acids wherein each of the organicacids has one of the general structural formulas 16:1; 18:0; and 18:1,with two thirds of the organic acids sharing the general formula 18:1being branched, and with about half of the branched organic acidsdiffering from each other by degree of branching (e.g., sub-branches)and/or by branch length (methyl, ethyl, etc.).

In yet another example, the diverse mixture of organic acids mayincorporate nineteen organic acids having the following generalformulas: 1) C16:0; 2) C17:0; 3) C17:0; 4) C17:0; 5) C18:0; 6) C18:0; 7)C18:0; 8) C18:1; 9) C18:1; 10) C18:1; 11) C18:1; 12) C18:1; 13) C18:1;14) C18:2; 15) C18:2; 16) C18:3; 17) C18:3; 18) C19:0; 19) C19:0; 20)C20:0; 21) C20:0. In this embodiment, organic acids 2, 3, and 4 sharethe same general structural formula but have different chemical andphysical properties due to other different characteristics. This islikewise true of organic acids 5, 6, and 7; as well as organic acids 8,9, 10, 11, 12, and 13; as well as organic acids 14 and 15; as well asorganic acids 16 and 17; as well as organic acids 18 and 19; as well asorganic acids 20 and 21.

In still another embodiment, the diverse mixture of organic acids mayincorporate at least ten organic acids having the following generalformulas 1) C16:0; 2) C17:0; 3) C17:0; 4) C18:0; 5) C18:1; 6) C18:2; 7)C18:2; 8) C18:2; 9) C18:3; 10) C19:1. In this embodiment, organic acids2 and 3 share the same general structural formula but have differentgeometrical configurations. This is likewise true of organic acids 6, 7,and 8 of this example.

In an alternative embodiment, a diverse mixture of organic acidsincorporates ten organic acids wherein each has 18 carbons in itsrespective carbon chain but the organic acids nevertheless differ withrespect to at least one of: number of double bonds on carbon chains;positioning of acid groups on carbon chains; hydrogen configurations onthe carbon chains; presence/absence of functional groups on carbonchains, types of functional groups on carbon chains, differentfunctional groups on carbon chains; being conjugated/non-conjugated; orcombinations thereof.

Conjugated organic acids have at least one pair of double bondsseparated by one single bond. Meanwhile, hydrogen configurations oforganic acids differ where a first organic acid has a cis configurationand a second organic acid has a trans configuration. Moreover, organicacids can have acid groups in different locations/positions on theirrespective carbon chains where, for example, a first organic acid isprimary acid, namely the acid group is located on the end of the carbonchain, whereas a second organic acid is secondary (iso) or tertiary,etc. acid.

Organic acids can have different functional groups such as —OH (e.g.,ricinoleic acid), —COOH (e.g., adipic acid), or —NH₂ (e.g., an aminoacid). Further, a first organic acid may be an aliphatic fatty acid,whereas a second organic acid is an aromatic acid such as benzoic acid.

Meanwhile, the relative amounts or concentrations of each organic acidcontained in a highly diverse mixture can be adjusted in order tofurther target desired golf ball properties such as by adding a pureorganic acid (e.g., oleic) to the highly diverse mixture. In oneembodiment, no single organic acid is present in the highly diversemixture in a concentration greater than 80%. In another embodiment, nosingle organic acid is present in the highly diverse mixture in aconcentration greater than 60%. In yet another embodiment, no singleorganic acid is present in the highly diverse mixture in a concentrationgreater than 40%.

In one embodiment, at least one organic acid is present in the highlydiverse mixture in a concentration greater than 20% and not greater than80%. In another embodiment, at least one organic acid is present in thehighly diverse mixture in a concentration greater than 20% and nogreater than 60%. In yet another embodiment, at least one organic acidis present in the highly diverse mixture in a concentration greater than20% and no greater than 40%.

In still another embodiment, at least one organic acid is present in thehighly diverse mixture in a concentration of from about 40% to 80%. Inan alternative embodiment, at least one organic acid is present in thehighly diverse mixture in a concentration of from about 60% to 80%. In adifferent embodiment, at least one organic acid is present in the highlydiverse mixture in a concentration of from about 40% to 60%. Embodimentsare also envisioned wherein, for example, at least one organic acid ispresent in the highly diverse mixture in a concentration of from about30% to about 40%, and/or at least one organic acid is present in thehighly diverse mixture in a concentration of from about 50% to about60%.

In one embodiment, branched organic acids are present in the highlydiverse mixture in a concentration of at least 40%. In one particularembodiment, branched organic acids are present in the highly diversemixture in a concentration of at least 40% and each other organic acidis present in concentrations less than 40%. For example, in oneembodiment, a branched organic acid may be present in the highly diversemixture in a concentration of at least 40%, whereas three other organicacids are present in the highly diverse mixture in concentrations of30-40%, 10-20%, and less than 10%.

In one embodiment, conjugated organic acids are present in the highlydiverse mixture in a concentration of at least 50% and non-conjugatedorganic acids are present in the highly diverse mixture in aconcentration of up to 10%.

In some embodiments, the highly diverse mixture may contain one or morepredominant organic acids, with the other organic acids of the highlydiverse mixture being present in concentrations that differ from eachother by no greater than 5%, or by less than about 5%, or by less than5%, or by no greater than 7%, or by less than about 7%, or by less than7%, or by no greater than 10%, or by less than about 10%, or by lessthan 10%, or by no greater than 15%, or by less than about 15%, or byless than 15%. In other embodiments, the other organic acids of themixture may differ from each other by up to about 5%, or by up to 5%, orby up to about 7%, or by up to 7%, or by up to about 10%, or by up to10%; or by up to about 15%, or by up to 15%.

For example, in one embodiment, the HNP composition may comprise amixture of at least one ethylene acid copolymer; a sufficient amount ofcation source to neutralize greater than about 100% of all acid groupspresent; and a highly diverse mixture of from three to about forty fivedifferent organic acids, with two to four organic acids being present ina collective concentration of from about 40% to about 80% of the mixtureand wherein up to 43 other organic acids are present in concentrationsthat differ from each other by no greater than about 5%, or 7%, or 10%,or 15%.

Non-limiting examples of suitable organic acids are, for example,aliphatic organic acids, aromatic organic acids, saturatedmonofunctional organic acids, unsaturated monofunctional organic acids,multi-unsaturated monofunctional organic acids, and dimerizedderivatives thereof. Particular examples of suitable organic acidsinclude, but are not limited to, caproic acid, caprylic acid, capricacid, lauric acid, stearic acid, behenic acid, erucic acid, oleic acid,linoleic acid, myristic acid, benzoic acid, palmitic acid, phenylaceticacid, naphthalenoic acid, sulfonic acids, phosphonic/phosphinic acid,dimerized derivatives thereof, and combinations thereof. Salts oforganic acids comprise the salts, particularly the barium, lithium,sodium, zinc, bismuth, chromium, cobalt, copper, potassium, stontium,titanium, tungsten, magnesium, aluminum, and calcium salts, of aliphaticorganic acids, aromatic organic acids, saturated monofunctional organicacids, unsaturated monofunctional organic acids, multi-unsaturatedmonofunctional organic acids, dimerized derivatives thereof, andcombinations thereof. Suitable organic acids and salts thereof are morefully described, for example, in U.S. Pat. No. 6,756,436, the entiredisclosure of which is hereby incorporated herein by reference.

Meanwhile, suitable cation sources include metal ions and compounds ofalkali metals, alkaline earth metals, and transition metals; metal ionsand compounds of rare earth elements; silicone, silane, and silicatederivatives and complex ligands; and combinations thereof. Preferredcation sources are metal ions and compounds of magnesium, sodium,potassium, cesium, calcium, barium, manganese, copper, zinc, tin,lithium, and rare earth metals. The acid copolymer may be at leastpartially neutralized prior to contacting the acid copolymer with thecation source to form the HNP. Methods of preparing ionomers are wellknown, and are disclosed, for example, in U.S. Pat. No. 3,264,272, theentire disclosure of which is hereby incorporated herein by reference.The acid copolymer can be a direct copolymer wherein the polymer ispolymerized by adding all monomers simultaneously, as disclosed, forexample, in U.S. Pat. No. 4,351,931, the entire disclosure of which ishereby incorporated herein by reference. Alternatively, the acidcopolymer can be a graft copolymer wherein a monomer is grafted onto anexisting polymer, as disclosed, for example, in U.S. Patent ApplicationPublication No. 2002/0013413, the entire disclosure of which is herebyincorporated herein by reference.

For purposes of the present disclosure, material hardness is measuredaccording to ASTM D2240 and generally involves measuring the hardness ofa flat “slab” or “button” formed of the material. It should beunderstood that there is a fundamental difference between “materialhardness” and “hardness as measured directly on a golf ball.” Hardnessas measured directly on a golf ball (or other spherical surface)typically results in a different hardness value than material hardness.This difference in hardness values is due to several factors including,but not limited to, ball construction (i.e., core type, number of coreand/or cover layers, etc.), ball (or sphere) diameter, and the materialcomposition of adjacent layers. It should also be understood that thetwo measurement techniques are not linearly related and, therefore, onehardness value cannot easily be correlated to the other. Unless statedotherwise, the hardness values given herein for cover materials arematerial hardness values measured according to ASTM D2240, with allvalues reported following 10 days of aging at 50% relative humidity and23° C.

The surface hardness of a golf ball layer is obtained from the averageof a number of measurements taken from opposing hemispheres of a core,taking care to avoid making measurements on the parting line of the coreor on surface defects, such as holes or protrusions. Hardnessmeasurements are made pursuant to ASTM D-2240 “Indentation Hardness ofRubber and Plastic by Means of a Durometer.” Because of the curvedsurface of a core, care must be taken to insure that the golf ball orgolf ball subassembly is centered under the durometer indentor before asurface hardness reading is obtained. A calibrated, digital durometer,capable of reading to 0.1 hardness units is used for all hardnessmeasurements and is set to take hardness readings at 1 second after themaximum reading is obtained. The digital durometer must be attached to,and its foot made parallel to, the base of an automatic stand, such thatthe weight on the durometer and attack rate conform to ASTM D-2240.

The center hardness of a core is obtained according to the followingprocedure. The core is gently pressed into a hemispherical holder havingan internal diameter approximately slightly smaller than the diameter ofthe core, such that the core is held in place in the hemisphericalportion of the holder while concurrently leaving the geometric centralplane of the core exposed. The core is secured in the holder byfriction, such that it will not move during the cutting and grindingsteps, but the friction is not so excessive that distortion of thenatural shape of the core would result. The core is secured such thatthe parting line of the core is roughly parallel to the top of theholder. The diameter of the core is measured 90 degrees to thisorientation prior to securing. A measurement is also made from thebottom of the holder to the top of the core to provide a reference pointfor future calculations. A rough cut, made slightly above the exposedgeometric center of the core using a band saw or other appropriatecutting tool, making sure that the core does not move in the holderduring this step. The remainder of the core, still in the holder, issecured to the base plate of a surface grinding machine. The exposed‘rough’ surface is ground to a smooth, flat surface, revealing thegeometric center of the core, which can be verified by measuring theheight of the bottom of the holder to the exposed surface of the core,making sure that exactly half of the original height of the core, asmeasured above, has been removed to within ±0.004 inches. Leaving thecore in the holder, the center of the core is found with a center squareand carefully marked and the hardness is measured at the center mark.

Golf ball core layers of the present invention may have a zero ornegative or positive hardness gradient. A hardness gradient is definedby hardness measurements made at the surface of the layer (e.g., center,outer core layer, etc.) and radially inward towards the center of theball, typically at 2 mm increments. For purposes of the presentinvention, “negative” and “positive” refer to the result of subtractingthe hardness value at the innermost portion of the golf ball componentfrom the hardness value at the outer surface of the component. Forexample, if the outer surface of a solid core has a lower hardness valuethan the center (i.e., the surface is softer than the center), thehardness gradient will be deemed a “negative” gradient. In measuring thehardness gradient of a core, the center hardness is first determinedaccording to the procedure above for obtaining the center hardness of acore. Once the center of the core is marked and the hardness thereof isdetermined, hardness measurements at any distance from the center of thecore may be measured by drawing a line radially outward from the centermark, and measuring and marking the distance from the center, typicallyin 2 mm increments. All hardness measurements performed on a planepassing through the geometric center are performed while the core isstill in the holder and without having disturbed its orientation, suchthat the test surface is constantly parallel to the bottom of theholder. The hardness difference from any predetermined location on thecore is calculated as the average surface hardness minus the hardness atthe appropriate reference point, e.g., at the center of the core for asingle, solid core, such that a core surface softer than its center willhave a negative hardness gradient. Hardness gradients are disclosed morefully, for example, in U.S. patent application Ser. No. 11/832,163,filed on Aug. 1, 2007; Ser. No. 11/939,632, filed on Nov. 14, 2007; Ser.No. 11/939,634, filed on Nov. 14, 2007; Ser. No. 11/939,635, filed onNov. 14, 2007; and Ser. No. 11/939,637, filed on Nov. 14, 2007; theentire disclosure of each of these references is hereby incorporatedherein by reference.

The term “DCM compression”, as used herein, refers to compressions thatare determined using a Dynamic Compression Machine, which is capable ofcapturing compressions that fall outside the Atti compression scalerange of −75 to 200 (the DCM scale compression range is −246 to 200).The Dynamic Compression Machine (“DCM”) is an apparatus that applies aload to a core/ball/sphere and measures the number of inches thecore/ball/sphere is deflected at measured loads. A load/deflection curveis generated that is fit to the Atti compression scale that results in anumber being generated representing an Atti compression.

The DCM does this via a load cell attached to the bottom of a hydrauliccylinder that is triggered pneumatically at a fixed rate (typicallyabout 1.0 ft/s) towards a stationary core/ball/sphere. Attached to thecylinder is an LVDT that measures the distance the cylinder travelsduring the testing timeframe. A software-based logarithmic algorithmensures that measurements are not taken until at least five successiveincreases in load are detected during the initial phase of the test.

In the present invention, a solid sphere of inventive material generallytargets a DCM compression of from about 0 to about 150, but embodimentsare certainly envisioned wherein the desired DCM compression of a sphereof resulting material is from about −200 to about 200.

Meanwhile, in many embodiments, inventive materials may also of coursebe measured or described in terms of Atti compression. As disclosed inJeff Dalton's Compression by Any Other Name, Science and Golf IV,Proceedings of the World Scientific Congress of Golf (Eric Thain ed.,Routledge, 2002) (“J. Dalton”), several different methods can be used tomeasure compression, including Atti compression, Riehle compression,load/deflection measurements at a variety of fixed loads and offsets,and effective modulus. For purposes of the present invention,“compression” refers to Atti compression and is measured according to aknown procedure, using an Atti compression test device, wherein a pistonis used to compress a ball against a spring. The travel of the piston isfixed and the deflection of the spring is measured. The measurement ofthe deflection of the spring does not begin with its contact with theball; rather, there is an offset of approximately the first 1.25 mm(0.05 inches) of the spring's deflection. Very low stiffness cores willnot cause the spring to deflect by more than 1.25 mm and therefore havea zero compression measurement. The Atti compression tester is designedto measure objects having a diameter of 42.7 mm (1.68 inches); thus,smaller objects, such as golf ball cores, must be shimmed to a totalheight of 42.7 mm to obtain an accurate reading. Conversion from Atticompression to Riehle (cores), Riehle (balls), 100 kg deflection, 130-10kg deflection or effective modulus can be carried out according to theformulas given in J. Dalton.

The material of the at least one layer of the present inventiontypically has a coefficient of restitution (“CoR”) at 125 ft/s of atleast 0.800, or at least 0.803. CoR, which can be determined accordingto a known procedure wherein a golf ball or golf ball subassembly (e.g.,a golf ball core or other spherical component) is fired from an aircannon at a given velocity (125 ft/s for purposes of the presentinvention). Ballistic light screens are located between the air cannonand the steel plate to measure ball velocity. As the sphere travelstoward the steel plate, it activates each light screen, and the time ateach light screen is measured. This provides an incoming transit timeperiod proportional to the ball's incoming velocity. The sphere impactsthe steel plate and rebounds through the light screens, which againmeasure the time period required to transit between the light screens.This provides an outgoing transit time period proportional to the ball'soutgoing velocity. CoR is then calculated as the ratio of the outgoingtransit time period to the incoming transit time period,CoR=T_(out)/T_(in).

In an alternative embodiment, a golf ball of the invention may compriseat least one layer that consists of the HNP composition consisting of amixture of: at least one ethylene acid copolymer; a sufficient amount ofcation source to neutralize greater than about 100% of all acid groupspresent; and a highly diverse mixture of organic acids.

Regardless, the at least one layer of golf ball of the invention maycomprise a relatively soft, or relatively low modulus HNP composition;or a relatively hard, or relatively high modulus HNP composition; orblends thereof. As used herein, “modulus” refers to flexural modulus asmeasured using a standard flex bar according to ASTM D790-B.

Relatively Soft/Low Modulus HNP Composition

Relatively soft HNP compositions may have a material hardness of 80Shore D or less, and preferably have a Shore D hardness of 55 or less ora Shore D hardness within the range having a lower limit of 10 or 20 or30 or 37 or 39 or 40 or 45 and an upper limit of 48 or 50 or 52 or 55 or60 or 80. Alternatively, soft HNP compositions may have a materialhardness within a range having a lower limit of 30 or 40 or 45 Shore Cand an upper limit of 55 or 60 or 80 Shore C.

Low modulus HNP compositions may comprise at least one low modulus HNPhaving a modulus within a range having a lower limit of 1,000 or 5,000or 10,000 psi and an upper limit of 17,000 or 25,000 or 28,000 or 30,000or 35,000 or 45,000 or 50,000 or 55,000 psi. In a preferred embodiment,the modulus of the low modulus HNP is at least 10% less, or at least 20%less, or at least 25% less, or at least 30% less, or at least 35% less,than the modulus of the high modulus HNP.

Relatively soft HNP compositions may comprise at least one highlyneutralized acid polymer. In a preferred embodiment, the highlyneutralized acid polymer of the relatively soft HNP composition is a lowmodulus HNP having a modulus within a range having a lower limit of1,000 or 5,000 or 10,000 psi and an upper limit of 17,000 or 25,000 or28,000 or 30,000 or 35,000 or 45,000 or 50,000 or 55,000 psi. In aparticular aspect of this embodiment, the modulus of the low modulus HNPis at least 10% less, or at least 20% less, or at least 25% less, or atleast 30% less, or at least 35% less, than that of the high modulus HNPdiscussed below.

HNPs of the relatively soft/low modulus HNP compositions may be salts ofacid copolymers. It is understood that the HNP may be a blend of two ormore HNPs. The acid copolymer of the HNP is an O/X/Y-type copolymer,wherein O is an α-olefin, X is a C₃-C₈ α,β-ethylenically unsaturatedcarboxylic acid, and Y is a softening monomer. O is preferably ethylene.X is preferably selected from (meth) acrylic acid, ethacrylic acid,maleic acid, crotonic acid, fumaric acid, and itaconic acid. (Meth)acrylic acid is particularly preferred. As used herein, “(meth) acrylicacid” means methacrylic acid and/or acrylic acid. Likewise, “(meth)acrylate” means methacrylate and/or acrylate. Y is preferably an alkyl(meth) acrylate, wherein the alkyl groups have from 1 to 8 carbon atoms.Preferred O/X/Y-type copolymers are those wherein O is ethylene, X is(meth) acrylic acid, and Y is selected from (meth) acrylate, n-butyl(meth) acrylate, isobutyl (meth) acrylate, methyl (meth) acrylate, andethyl (meth) acrylate. Particularly preferred O/X/Y-type copolymers areethylene/(meth) acrylic acid/n-butyl acrylate, ethylene/(meth) acrylicacid/methyl acrylate, and ethylene/(meth) acrylic acid/ethyl acrylate.

The acid copolymer of the HNP typically includes the α-olefin in anamount of at least 15 wt %, or at least 25 wt %, or at least 40 wt %, orat least 60 wt %, based on the total weight of the acid copolymer. Theamount of C₃-C₈ α,β-ethylenically unsaturated carboxylic acid in theacid copolymer is typically within a range having a lower limit of 1 or2 or 4 or 6 or 8 or 10 or 12 or 15 or 16 or 20 wt % and an upper limitof 20 or 25 or 26 or 30 or 35 or 40 wt %, based on the total weight ofthe acid copolymer. The amount of optional softening monomer in the acidcopolymer is typically within a range having a lower limit of 0 or 1 or3 or 5 or 11 or 15 or 20 wt % and an upper limit of 23 or 25 or 30 or 35or 50 wt %, based on the total weight of the acid copolymer.

Particularly suitable acid copolymers of the HNP of the relativelysoft/low modulus HNP composition include very low modulusionomer-(“VLMI-”) type ethylene-acid polymers, such as Surlyn® 6320,Surlyn® 8120, Surlyn® 8320, and Surlyn® 9320. Surlyn® ionomers arecommercially available from E. I. du Pont de Nemours and Company. Alsosuitable are DuPont® HPF 1000, HPF 2000, HPF AD 1035, HPF AD 1040,ionomeric materials commercially available from E. I. du Pont de Nemoursand Company.

Additional suitable acid copolymers are disclosed, for example, in U.S.Patent Application Publication Nos. 2005/0148725, 2005/0020741,2004/0220343, and 2003/0130434, and U.S. Pat. Nos. 5,691,418, 6,562,906,6,653,382, 6,777,472, 6,762,246, and 6,815,480, the entire disclosuresof which are hereby incorporated herein by reference.

In a preferred embodiment, the HNP of the relatively soft/low modulusHNP composition is formed by reacting an acid copolymer, which isoptionally partially neutralized, with a sufficient amount of cationsource, in the presence of an organic acid or salt thereof, such that atleast 80%, preferably at least 90%, more preferably at least 95%, andeven more preferably 100%, of all acid groups present are neutralized.In a particular embodiment, the cation source is present in an amountsufficient to neutralize, theoretically, greater than 100%, or 105% orgreater, or 110% or greater, or 115% or greater, or 120% or greater, or125% or greater, or 200% or greater, or 250% or greater of all acidgroups present in the composition. The acid copolymer can be reactedwith the organic acid or salt thereof and the cation sourcesimultaneously, or the acid copolymer can be reacted with the organicacid prior to the addition of the cation source.

Suitable organic acids are aliphatic organic acids, aromatic organicacids, saturated monofunctional organic acids, unsaturatedmonofunctional organic acids, multi-unsaturated monofunctional organicacids, and dimerized derivatives thereof. Particular examples ofsuitable organic acids include, but are not limited to, caproic acid,caprylic acid, capric acid, lauric acid, stearic acid, behenic acid,erucic acid, oleic acid, linoleic acid, myristic acid, benzoic acid,palmitic acid, phenylacetic acid, naphthalenoic acid, sulfonic acids,phosphonic/phosphinic acid, dimerized derivatives thereof, andcombinations thereof. Salts of organic acids comprise the salts,particularly the barium, lithium, sodium, zinc, bismuth, chromium,cobalt, copper, potassium, stontium, titanium, tungsten, magnesium,aluminum and calcium salts, of aliphatic organic acids, aromatic organicacids, saturated monofunctional organic acids, unsaturatedmonofunctional organic acids, multi-unsaturated monofunctional organicacids, dimerized derivatives thereof, and combinations thereof. Suitableorganic acids and salts thereof are more fully described, for example,in U.S. Pat. No. 6,756,436, the entire disclosure of which is herebyincorporated herein by reference.

Suitable cation sources include metal ions and compounds of alkalimetals, alkaline earth metals, and transition metals; metal ions andcompounds of rare earth elements; silicone, silane, and silicatederivatives and complex ligands; and combinations thereof. Preferredcation sources are metal ions and compounds of magnesium, sodium,potassium, cesium, calcium, barium, manganese, copper, zinc, tin,lithium, and rare earth metals. The acid copolymer may be at leastpartially neutralized prior to contacting the acid copolymer with thecation source to form the HNP. Methods of preparing ionomers are wellknown, and are disclosed, for example, in U.S. Pat. No. 3,264,272, theentire disclosure of which is hereby incorporated herein by reference.The acid copolymer can be a direct copolymer wherein the polymer ispolymerized by adding all monomers simultaneously, as disclosed, forexample, in U.S. Pat. No. 4,351,931, the entire disclosure of which ishereby incorporated herein by reference. Alternatively, the acidcopolymer can be a graft copolymer wherein a monomer is grafted onto anexisting polymer, as disclosed, for example, in U.S. Patent ApplicationPublication No. 2002/0013413, the entire disclosure of which is herebyincorporated herein by reference.

Relatively soft/low modulus HNP compositions optionally contain one ormore melt flow modifiers. The amount of melt flow modifier in thecomposition is readily determined such that the melt flow index of thecomposition is at least 0.1 g/10 min, preferably from 0.5 g/10 min to10.0 g/10 min, and more preferably from 1.0 g/10 min to 6.0 g/10 min, asmeasured using ASTM D-1238, condition E, at 190° C., using a 2160 gramweight.

Suitable melt flow modifiers include, but are not limited to, organicacids and salts thereof, polyamides, polyesters, polyacrylates,polyurethanes, polyethers, polyureas, polyhydric alcohols, andcombinations thereof. Suitable organic acids are aliphatic organicacids, aromatic organic acids, saturated mono-functional organic acids,unsaturated monofunctional organic acids, multi-unsaturatedmono-functional organic acids, and dimerized derivatives thereof.Particular examples of suitable organic acids include, but are notlimited to, caproic acid, caprylic acid, capric acid, lauric acid,stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid,myristic acid, benzoic acid, palmitic acid, phenylacetic acid,naphthalenoic acid, sulfonic acids, phosphonic/phosphinic acid,dimerized derivatives thereof, and combinations thereof. Suitableorganic acids are more fully described, for example, in U.S. Pat. No.6,756,436, the entire disclosure of which is hereby incorporated hereinby reference. In a particular embodiment, the HNP composition comprisesan organic acid salt in an amount of 20 phr or greater, or 25 phr orgreater, or 30 phr or greater, or 35 phr or greater, or 40 phr orgreater.

Additional melt flow modifiers suitable for use include the non-fattyacid melt flow modifiers described in copending U.S. patent applicationSer. Nos. 11/216,725 and 11/216,726, the entire disclosures of which arehereby incorporated herein by reference.

Relatively soft/low modulus HNP compositions optionally includeadditive(s) and/or filler(s) in an amount of 50 wt % or less, or 30 wt %or less, or 15 wt % or less, based on the total weight of the relativelysoft/low modulus HNP composition. Suitable additives and fillersinclude, but are not limited to, chemical blowing and foaming agents,optical brighteners, coloring agents, fluorescent agents, whiteningagents, UV absorbers, light stabilizers, defoaming agents, processingaids, mica, talc, nano-fillers, antioxidants, stabilizers, softeningagents, fragrance components, plasticizers, impact modifiers, TiO₂, acidcopolymer wax, surfactants, and fillers, such as zinc oxide, tin oxide,barium sulfate, zinc sulfate, calcium oxide, calcium carbonate, zinccarbonate, barium carbonate, clay, tungsten, tungsten carbide, silica,lead silicate, regrind (recycled material), and mixtures thereof.Suitable additives are more fully described in, for example, U.S. PatentApplication Publication No. 2003/0225197, the entire disclosure of whichis hereby incorporated herein by reference.

Relatively soft/low modulus HNP compositions optionally contain a highmodulus HNP.

In a particular embodiment, the relatively soft/low modulus HNPcomposition has a moisture vapor transmission rate of 8 g-mil/100in²/day or less (i.e., 3.2 g-mm/m²·day or less), or 5 g-mil/100 in²/dayor less (i.e., 2.0 g-mm/m²·day or less), or 3 g-mil/100 in²/day or less(i.e., 1.2 g-mm/m²·day or less), or 2 g-mil/100 in²/day or less (i.e.,0.8 g-mm/m²·day or less), or 1 g-mil/100 in²/day or less (i.e., 0.4g-mm/m²·day or less), or less than 1 g-mil/100 in²/day (i.e., less than0.4 g-mm/m²·day). As used herein, moisture vapor transmission rate(“MVTR”) is given in g-mil/100 in²/day, and is measured at 20° C. andaccording to ASTM F1249-99. In a preferred aspect of this embodiment,the relatively soft/low modulus HNP composition comprises a low modulusHNP prepared using a cation source which is less hydrophilic thanconventional magnesium-based cation sources. Suitable moisture resistantHNP compositions are disclosed, for example, in U.S. Patent ApplicationPublication Nos. 2005/0267240, 2006/0106175 and 2006/0293464, the entiredisclosures of which are hereby incorporated herein by reference.

In another particular embodiment, a sphere formed from the relativelysoft/low modulus HNP composition has a compression of 80 or less, or 70or less, or 65 or less, or 60 or less, or 50 or less, or 40 or less, or30 or less, or 20 or less.

Relatively soft/low modulus HNP compositions are not limited by anyparticular method or any particular equipment for making thecompositions. In a preferred embodiment, the composition is prepared bythe following process. The acid polymer(s), preferably a VLMI-typeethylene-acid terpolymer, organic acid(s) or salt(s) thereof, andoptionally additive(s)/filler(s) are simultaneously or individually fedinto a melt extruder, such as a single or twin screw extruder. Asuitable amount of cation source is simultaneously or subsequently addedsuch that at least 80%, preferably at least 90%, more preferably atleast 95%, and even more preferably at least 100%, of all acid groupspresent are neutralized. Optionally, the cation source is added in anamount sufficient to neutralize, theoretically, 105% or greater, or 110%or greater, or 115% or greater, or 120% or greater, or 125% or greater,or 200% or greater, or 250% or greater of all acid groups present in thecomposition. The acid polymer may be at least partially neutralizedprior to the above process. The components are intensively mixed priorto being extruded as a strand from the die-head.

Relatively soft/low modulus HNP compositions optionally comprise one ormore additional polymers, such as partially neutralized ionomers (e.g.,as disclosed in U.S. Patent Application Publication No. 2006/0128904,the entire disclosure of which is hereby incorporated herein byreference); bimodal ionomers (e.g., as disclosed in U.S. PatentApplication Publication No. 2004/0220343 and U.S. Pat. Nos. 6,562,906,6,762,246, 7,273,903, 8,193,283, 8,410,219, and 8,410,220, the entiredisclosures of which are hereby incorporated herein by reference, andparticularly Surlyn® AD 1043, 1092, and 1022 ionomer resins,commercially available from E. I. du Pont de Nemours and Company);ionomers modified with rosins (e.g., as disclosed in U.S. PatentApplication Publication No. 2005/0020741, the entire disclosure of whichis hereby incorporated by reference); soft and resilient ethylenecopolymers (e.g., as disclosed U.S. Patent Application Publication No.2003/0114565, the entire disclosure of which is hereby incorporatedherein by reference); polyolefins; polyamides; polyesters; polyethers;polycarbonates; polysulfones; polyacetals; polylactones;acrylonitrile-butadiene-styrene resins; polyphenylene oxide;polyphenylene sulfide; styrene-acrylonitrile resins; styrene maleicanhydride; polyimides; aromatic polyketones; ionomers and ionomericprecursors, acid copolymers, and conventional HNPs; polyurethanes;grafted and non-grafted metallocene-catalyzed polymers; single-sitecatalyst polymerized polymers; high crystalline acid polymers; cationicionomers; natural and synthetic rubbers, including, but not limited to,ethylene propylene rubber (“EPR”), ethylene propylene diene rubber(“EPDM”), styrenic block copolymer rubbers (such as SI, SIS, SB, SBS,SIBS, and the like, where “S” is styrene, “I” is isobutylene, and “B” isbutadiene), butyl rubber, halobutyl rubber, copolymers of isobutyleneand para-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene, natural rubber, polyisoprene, copolymers of butadienewith acrylonitrile, polychloroprene, alkyl acrylate rubber (such asethylene-alkyl acrylates and ethylene-alkyl methacrylates, and, morespecifically, ethylene-ethyl acrylate, ethylene-methyl acrylate, andethylene-butyl acrylate), chlorinated isoprene rubber, acrylonitrilechlorinated isoprene rubber, and polybutadiene rubber (cis and trans);and combinations thereof. Particular polyolefins suitable for blendinginclude one or more, linear, branched, or cyclic, C₂-C₄₀ olefins,particularly polymers comprising ethylene or propylene copolymerizedwith one or more C₂-C₄₀ olefins, C₃-C₂₀ α-olefins, or C₃-C₁₀ α-olefins.Particular conventional HNPs suitable for blending include, but are notlimited to, one or more of the HNPs disclosed in U.S. Pat. Nos.6,756,436, 6,894,098, and 6,953,820, the entire disclosures of which arehereby incorporated herein by reference. Additional suitable blendpolymers include those described in U.S. Pat. No. 5,981,658, for exampleat column 14, lines 30 to 56, the entire disclosure of which is herebyincorporated herein by reference. The blends described herein may beproduced by post-reactor blending, by connecting reactors in series tomake reactor blends, or by using more than one catalyst in the samereactor to produce multiple species of polymer. The polymers may bemixed prior to being put into an extruder, or they may be mixed in anextruder. In a particular embodiment, the HNP composition comprises anacid copolymer and an additional polymer component, wherein theadditional polymer component is a non-acid polymer present in an amountof greater than 50 wt %, or an amount within a range having a lowerlimit of 50 or 55 or 60 or 65 or 70 and an upper limit of 80 or 85 or90, based on the combined weight of the acid copolymer and the non-acidpolymer. In another particular embodiment, the HNP composition comprisesan acid copolymer and an additional polymer component, wherein theadditional polymer component is a non-acid polymer present in an amountof less than 50 wt %, or an amount within a range having a lower limitof 10 or 15 or 20 or 25 or 30 and an upper limit of 40 or 45 or 50,based on the combined weight of the acid copolymer and the non-acidpolymer.

Particularly suitable relatively soft/low modulus HNP compositionsinclude, but are not limited to, the highly-resilient thermoplasticcompositions disclosed in U.S. Patent Application Publication No.2005/0148725; the highly-neutralized ethylene copolymers disclosed inU.S. Pat. Nos. 6,653,382 and 6,777,472, and U.S. Patent ApplicationPublication No. 2003/0130434; and the highly-resilient thermoplasticelastomer compositions disclosed in U.S. Pat. No. 6,815,480; the entiredisclosures of which are hereby incorporated herein by reference.

In a particular embodiment, the relatively soft/low modulus HNPcomposition is formed by blending an acid polymer, a non-acid polymer, acation source, and a highly diverse mixture of organic acids. Forpurposes of the present invention, maleic anhydride modified polymersare defined herein as a non-acid polymer despite having anhydride groupsthat can ring-open to the acid form during processing of the polymer toform the HNP compositions herein. The maleic anhydride groups aregrafted onto a polymer, are present at relatively very low levels, andare not part of the polymer backbone, as is the case with the acidpolymers, which are exclusively E/X and E/X/Y copolymers of ethylene andan acid, particularly methacrylic acid and acrylic acid.

In a particular aspect of this embodiment, the acid polymer is selectedfrom ethylene-acrylic acid and ethylene-methacrylic acid copolymers,optionally containing a softening monomer selected from n-butyl acrylateand iso-butyl acrylate. The acid polymer preferably has an acid contentwith a range having a lower limit of 2 or 10 or 15 or 16 mol % and anupper limit of 20 or 25 or 26 or 30 mol %. Examples of particularlysuitable commercially available acid polymers include, but are notlimited to, those given in Table 3 below.

TABLE 3 Melt Index Softening (2.16 kg, Acid Monomer 190° C., AcidPolymer (wt %) (wt %) g/10 min) Nucrel ® 9-1 methacrylic acid n-butylacrylate 25 (9.0) (23.5) Nucrel ® 599 methacrylic acid none 450 (10.0)Nucrel ® 960 methyacrylic acid none 60 (15.0) Nucrel ® 0407 methacrylicacid none 7.5 (4.0) Nucrel ® 0609 methacrylic acid none 9 (6.0) Nucrel ®1214 methacrylic acid none 13.5 (12.0) Nucrel ® 2906 methacrylic acidnone 60 (19.0) Nucrel ® 2940 methacrylic acid none 395 (19.0) Nucrel ®30707 acrylic acid none 7 (7.0) Nucrel ® 31001 acrylic acid none 1.3(9.5) Nucrel ® AE methacrylic acid isobutyl acrylate 11 (2.0) (6.0)Nucrel ® 2806 acrylic acid none 60 (18.0) Nucrel ® 0403 methacrylic acidnone 3 (4.0) Nucrel ® 925 methacrylic acid none 25 (15.0) Escor ® AT-310acrylic acid methyl acrylate 6 (6.5) (6.5) Escor ® AT-325 acrylic acidmethyl acrylate 20 (6.0) (20.0) Escor ® AT-320 acrylic acid methylacrylate 5 (6.0) (18.0) Escor ® 5070 acrylic acid none 30 (9.0) Escor ®5100 acrylic acid none 8.5 (11.0) Escor ® 5200 acrylic acid none 38(15.0) A-C ® 5120 acrylic acid none not reported (15) A-C ® 540 acrylicacid none not reported (5) A-C ® 580 acrylic acid none not reported (10)Primacor ® 3150 acrylic acid none 5.8 (6.5) Primacor ® 3330 acrylic acidnone 11 (3.0) Primacor ® 5985 acrylic acid none 240 (20.5) Primacor ®5986 acrylic acid none 300 (20.5) Primacor ® 5980I acrylic acid none 300(20.5) Primacor ® 5990I acrylic acid none 1300 (20.0) XUS 60751.17acrylic acid none 600 (19.8) XUS 60753.02L acrylic acid none 60 (17.0)

Nucrel® acid polymers are commercially available from E. I. du Pont deNemours and Company.

Escor® acid polymers are commercially available from ExxonMobil ChemicalCompany.

A-C® acid polymers are commercially available from HoneywellInternational Inc.

Primacor® acid polymers and XUS acid polymers are commercially availablefrom The Dow Chemical Company.

In another particular aspect of this embodiment, the non-acid polymer isan elastomeric polymer. Suitable elastomeric polymers include, but arenot limited to:

(a) ethylene-alkyl acrylate polymers, particularly polyethylene-butylacrylate, polyethylene-methyl acrylate, and polyethylene-ethyl acrylate;

(b) metallocene-catalyzed polymers;

(c) ethylene-butyl acrylate-carbon monoxide polymers and ethylene-vinylacetate-carbon monoxide polymers;

(d) polyethylene-vinyl acetates;

(e) ethylene-alkyl acrylate polymers containing a cure site monomer;

(f) ethylene-propylene rubbers and ethylene-propylene-diene monomerrubbers;

(g) olefinic ethylene elastomers, particularly ethylene-octene polymers,ethylene-butene polymers, ethylene-propylene polymers, andethylene-hexene polymers;

(h) styrenic block copolymers;

(i) polyester elastomers;

(j) polyamide elastomers;

(k) polyolefin rubbers, particularly polybutadiene, polyisoprene, andstyrene-butadiene rubber; and

(l) thermoplastic polyurethanes.

Examples of particularly suitable commercially available non-acidpolymers include, but are not limited to, Lotader® ethylene-alkylacrylate polymers and Lotryl® ethylene-alkyl acrylate polymers, andparticularly Lotader® 4210, 4603, 4700, 4720, 6200, 8200, and AX8900commercially available from Arkema Corporation; Elvaloy® ACethylene-alkyl acrylate polymers, and particularly AC 1224, AC 1335, AC2116, AC3117, AC3427, and AC34035, commercially available from E. I. duPont de Nemours and Company; Fusabond® elastomeric polymers, such asethylene vinyl acetates, polyethylenes, metallocene-catalyzedpolyethylenes, ethylene propylene rubbers, and polypropylenes, andparticularly Fusabond® N525, C190, C250, A560, N416, N493, N614, P614,M603, E100, E158, E226, E265, E528, and E589, commercially availablefrom E. I. du Pont de Nemours and Company; Honeywell A-C polyethylenesand ethylene maleic anhydride copolymers, and particularly A-C 5180, A-C575, A-C 573, A-C 655, and A-C 395, commercially available fromHoneywell; Nordel® IP rubber, Elite® polyethylenes, Engage® elastomers,and Amplify® functional polymers, and particularly Amplify® GR 207, GR208, GR 209, GR 213, GR 216, GR 320, GR 380, and EA 100, commerciallyavailable from The Dow Chemical Company; Enable® metallocenepolyethylenes, Exact® plastomers, Vistamaxx® propylene-based elastomers,and Vistalon® EPDM rubber, commercially available from ExxonMobilChemical Company; Starflex® metallocene linear low density polyethylene,commercially available from LyondellBasell; Elvaloy® HP4051, HP441,HP661 and HP662 ethylene-butyl acrylate-carbon monoxide polymers andElvaloy® 741, 742 and 4924 ethylene-vinyl acetate-carbon monoxidepolymers, commercially available from E. I. du Pont de Nemours andCompany; Evatane® ethylene-vinyl acetate polymers having a vinyl acetatecontent of from 18 to 42%, commercially available from ArkemaCorporation; Elvax® ethylene-vinyl acetate polymers having a vinylacetate content of from 7.5 to 40%, commercially available from E. I. duPont de Nemours and Company; Vamac® G terpolymer of ethylene,methylacrylate and a cure site monomer, commercially available from E.I. du Pont de Nemours and Company; Vistalon® EPDM rubbers, commerciallyavailable from ExxonMobil Chemical Company; Kraton® styrenic blockcopolymers, and particularly Kraton® FG1901GT, FG1924GT, and RP6670GT,commercially available from Kraton Performance Polymers Inc.; Septon®styrenic block copolymers, commercially available from Kuraray Co.,Ltd.; Hytrel® polyester elastomers, and particularly Hytrel® 3078, 4069,and 556, commercially available from E. I. du Pont de Nemours andCompany; Riteflex® polyester elastomers, commercially available fromCelanese Corporation; Pebax® thermoplastic polyether block amides, andparticularly Pebax® 2533, 3533, 4033, and 5533, commercially availablefrom Arkema Inc.; Affinity® and Affinity® GA elastomers, Versify®ethylene-propylene copolymer elastomers, and Infuse® olefin blockcopolymers, commercially available from The Dow Chemical Company;Exxelor® polymer resins, and particularly Exxelor® PE 1040, PO 1015, PO1020, VA 1202, VA 1801, VA 1803, and VA 1840, commercially availablefrom ExxonMobil Chemical Company; and Royaltuf® EPDM, and particularlyRoyaltuf® 498 maleic anhydride modified polyolefin based on an amorphousEPDM and Royaltuf®485 maleic anhydride modified polyolefin based on ansemi-crystalline EPDM, commercially available from Chemtura Corporation.

Additional examples of particularly suitable commercially availableelastomeric polymers include, but are not limited to, those given inTable 4 below.

TABLE 4 Melt Index % Maleic (2.16 kg, 190° C., % Ester Anhydride g/10min) Polyethylene Butyl Acrylates Lotader ® 3210 6 3.1 5 Lotader ® 42106.5 3.6 9 Lotader ® 3410 17 3.1 5 Lotryl ® 17BA04 16-19 0 3.5-4.5Lotryl ® 35BA320 33-37 0 260-350 Elvaloy ® AC 3117 17 0 1.5 Elvaloy ® AC3427 27 0 4 Elvaloy ® AC 34035 35 0 40 Polyethylene Methyl AcrylatesLotader ® 4503 19 0.3 8 Lotader ® 4603 26 0.3 8 Lotader ® AX 8900 26 8%GMA 6 Lotryl ® 24MA02 23-26 0 1-3 Elvaloy ® AC 12024S 24 0 20 Elvaloy ®AC 1330 30 0 3 Elvaloy ® AC 1335 35 0 3 Elvaloy ® AC 1224 24 0 2Polyethylene Ethyl Acrylates Lotader ® 6200 6.5 2.8 40 Lotader ® 82006.5 2.8 200 Lotader ® LX 4110 5 3.0 5 Lotader ® HX 8290 17 2.8 70Lotader ® 5500 20 2.8 20 Lotader ® 4700 29 1.3 7 Lotader ® 4720 29 0.3 7Elvaloy ® AC 2116 16 0 1

The acid polymer and non-acid polymer are combined and reacted with acation source, such that at least 80% of all acid groups present areneutralized. The present invention is not meant to be limited by aparticular order for combining and reacting the acid polymer, non-acidpolymer and cation source. In a particular embodiment, the highlydiverse mixture of organic acids is used in an amount such that thehighly diverse mixture of organic acids is present in the HNPcomposition in an amount of from 10 wt % to 60 wt %, or within a rangehaving a lower limit of 10 or 20 or 30 or 40 wt % and an upper limit of40 or 50 or 60 wt %, based on the total weight of the HNP composition.Suitable cation sources and fatty acids and metal salts thereof arefurther disclosed above.

In another particular aspect of this embodiment, the acid polymer is anethylene-acrylic acid polymer having an acid content of 19 wt % orgreater, the non-acid polymer is a metallocene-catalyzed ethylene-butenecopolymer, optionally modified with maleic anhydride, the cation sourceis magnesium, and the highly diverse mixture of organic acids present inthe composition in an amount of 20 to 50 wt %, based on the total weightof the composition.

Relatively Hard/High Modulus HNP Composition

Relatively hard HNP compositions may have a Shore D hardness of 35 orgreater, and preferably have a Shore D hardness of 45 or greater or aShore D hardness with the range having a lower limit of 45 or 50 or 55or 57 or 58 or 60 or 65 or 70 or 75 and an upper limit of 80 or 85 or 90or 95. Alternatively, hard HNP compositions may have a material hardnesswithin a range having a lower limit of 65 or 70 or 75 Shore C and anupper limit of 85 or 90 or 95 Shore C.

High modulus HNP compositions may comprise at least one high modulus HNPhaving a modulus within a range having a lower limit of 25,000 or 27,000or 30,000 or 40,000 or 45,000 or 50,000 or 55,000 or 60,000 psi and anupper limit of 72,000 or 75,000 or 100,000 or 150,000 psi.

Relatively hard HNP compositions may comprise at least one highlyneutralized acid polymer. In a preferred embodiment, the highlyneutralized acid polymer of the relatively hard HNP composition is ahigh modulus HNP having a modulus within a range having a lower limit of25,000 or 27,000 or 30,000 or 40,000 or 45,000 or 50,000 or 55,000 or60,000 psi and an upper limit of 72,000 or 75,000 or 100,000 or 150,000psi.

HNPs of the relatively hard/high modulus HNP compositions may be saltsof acid copolymers. It is understood that the HNP may be a blend of twoor more HNPs. Preferred acid copolymers are copolymers of an α-olefinand a C₃-C₈ α,β-ethylenically unsaturated carboxylic acid. The acid istypically present in the acid copolymer in an amount within a rangehaving a lower limit of 1 or 2 or 4 or 6 or 8 or 10 or 12 or 15 or 16 or20 wt % and an upper limit of 20 or 25 or 26 or 30 or 35 or 40 wt %,based on the total weight of the acid copolymer. The α-olefin ispreferably selected from ethylene and propylene. The acid is preferablyselected from (meth) acrylic acid, ethacrylic acid, maleic acid,crotonic acid, fumaric acid, and itaconic acid. (Meth) acrylic acid isparticularly preferred. In a preferred embodiment, the HNP of therelatively hard HNP composition has a higher level of acid than the HNPof the relatively soft HNP composition.

Suitable acid copolymers include partially neutralized acid polymers.Examples of suitable partially neutralized acid polymers include, butare not limited to, Surlyn® ionomers, commercially available from E. I.du Pont de Nemours and Company; AClyn® ionomers, commercially availablefrom Honeywell International Inc.; and Iotek® ionomers, commerciallyavailable from ExxonMobil Chemical Company. Also suitable are DuPont®HPF 1000, HPF 2000, HPF AD 1035, HPF AD 1040, ionomeric materialscommercially available from E. I. du Pont de Nemours and Company.Additional suitable acid polymers are more fully described, for example,in U.S. Pat. Nos. 6,562,906, 6,762,246, and 6,953,820 and U.S. PatentApplication Publication Nos. 2005/0049367, 2005/0020741, and2004/0220343, the entire disclosures of which are hereby incorporatedherein by reference.

In a preferred embodiment, the HNP of the relatively hard/high modulusHNP composition is formed by reacting an acid copolymer, which mayalready be partially neutralized, with a sufficient amount of cationsource, optionally in the presence of an organic acid or salt thereof,such that at least 80%, preferably at least 90%, more preferably atleast 95%, and even more preferably 100%, of all acid groups present areneutralized. In a particular embodiment, the cation source is present inan amount sufficient to neutralize, theoretically, greater than 100%, or105% or greater, or 110% or greater, or 115% or greater, or 120% orgreater, or 125% or greater, or 200% or greater, or 250% or greater ofall acid groups present in the composition. Suitable cation sourcesinclude metal ions and compounds of alkali metals, alkaline earthmetals, and transition metals; metal ions and compounds of rare earthelements; silicone, silane, and silicate derivatives and complexligands; and combinations thereof. Preferred cation sources are metalions and compounds of magnesium, sodium, potassium, cesium, calcium,barium, manganese, copper, zinc, tin, lithium, aluminum, and rare earthmetals. Metal ions and compounds of calcium and magnesium areparticularly preferred. The acid copolymer may be at least partiallyneutralized prior to contacting the acid copolymer with the cationsource to form the HNP. As previously stated, methods of preparingionomers, and the acid copolymers on which ionomers are based, aredisclosed, for example, in U.S. Pat. Nos. 3,264,272, and 4,351,931, andU.S. Patent Application Publication No. 2002/0013413.

Relatively hard/high modulus HNP compositions may optionally contain oneor more melt flow modifiers. The amount of melt flow modifier in thecomposition is readily determined such that the melt flow index of thecomposition is at least 0.1 g/10 min, preferably from 0.5 g/10 min to10.0 g/10 min, and more preferably from 1.0 g/10 min to 6.0 g/10 min, asmeasured using ASTM D-1238, condition E, at 190° C., using a 2160 gramweight.

Suitable melt flow modifiers include, but are not limited to, organicacids and salts thereof, polyamides, polyesters, polyacrylates,polyurethanes, polyethers, polyureas, polyhydric alcohols, andcombinations thereof. Suitable organic acids are aliphatic organicacids, aromatic organic acids, saturated mono-functional organic acids,unsaturated monofunctional organic acids, multi-unsaturatedmono-functional organic acids, and dimerized derivatives thereof.Particular examples of suitable organic acids include, but are notlimited to, caproic acid, caprylic acid, capric acid, lauric acid,stearic acid, behenic acid, erucic acid, oleic acid, linoleic acid,myristic acid, benzoic acid, palmitic acid, phenylacetic acid,naphthalenoic acid, sulfonic acids, phosphonic/phosphinic acid,dimerized derivatives thereof and combinations thereof. Suitable organicacids are more fully described, for example, in U.S. Pat. No. 6,756,436,the entire disclosure of which is hereby incorporated herein byreference. In a particular embodiment, the HNP composition comprises anorganic acid salt in an amount of 20 phr or greater, or 25 phr orgreater, or 30 phr or greater, or 35 phr or greater, or 40 phr orgreater.

Additional melt flow modifiers suitable for use in compositions of thepresent invention, include the non-fatty acid melt flow modifiersdescribed in copending U.S. patent application Ser. Nos. 11/216,725 and11/216,726, the entire disclosures of which are hereby incorporatedherein by reference.

Relatively hard/high modulus HNP compositions may optionally includeadditive(s) and/or filler(s) in an amount within a range having a lowerlimit of 0 or 5 or 10 wt %, and an upper limit of 25 or 30 or 50 wt %,based on the total weight of the relatively hard/high modulus HNPcomposition. Suitable additives and fillers include those previouslydescribed as suitable for the relatively soft HNP compositions of thepresent invention.

Relatively hard/high modulus HNP compositions may optionally contain alow modulus HNP.

In a particular embodiment, the relatively hard/high modulus HNPcomposition has an MVTR of 8 g-mil/100 in²/day or less (i.e., 3.2g-mm/m²·day or less), or 5 g-mil/100 in²/day or less (i.e., 2.0g-mm/m²·day or less), or 3 g-mil/100 in²/day or less (i.e., 1.2g-mm/m²·day or less), or 2 g-mil/100 in²/day or less (i.e., 0.8g-mm/m²·day or less), or 1 g-mil/100 in²/day or less (i.e., 0.4g-mm/m²·day or less), or less than 1 g-mil/100 in²/day (i.e., less than0.4 g-mm/m²·day). In a preferred aspect of this embodiment, therelatively hard/high modulus HNP composition comprises a high modulusHNP prepared using a cation source which is less hydrophilic thanconventional magnesium-based cation sources. Suitable moisture resistantHNP compositions are disclosed, for example, in copending U.S. patentapplication Ser. No. 11/270,066 and U.S. Patent Application PublicationNo. 2005/0267240, the entire disclosures of which are herebyincorporated herein by reference.

In another particular embodiment, a sphere formed from the relativelyhard/high modulus HNP composition has a compression of 70 or greater, or80 or greater, or a compression within a range having a lower limit of70 or 80 or 90 or 100 and an upper limit of 110 or 130 or 140.

Relatively hard/high modulus HNP compositions are not limited by anyparticular method or any particular equipment for making thecompositions. In a preferred embodiment, the composition is prepared bythe following process. The acid polymer(s), preferably anethylene/(meth) acrylic acid copolymer, optional melt flow modifier(s),and optional additive(s)/filler(s) are simultaneously or individuallyfed into a melt extruder, such as a single or twin screw extruder. Asuitable amount of cation source is then added such that at least 80%,preferably at least 90%, more preferably at least 95%, and even morepreferably at least 100%, of all acid groups present are neutralized.Optionally, the cation source is added in an amount sufficient toneutralize, theoretically, 105% or greater, or 110% or greater, or 115%or greater, or 120% or greater, or 125% or greater, or 200% or greater,or 250% or greater of all acid groups present in the composition. Theacid polymer may be at least partially neutralized prior to the aboveprocess. The components are intensively mixed prior to being extruded asa strand from the die-head.

In another preferred embodiment, the relatively hard/high modulus HNPcomposition is formed by combining a low modulus HNP with a sufficientamount of one or more additional material(s), including, but not limitedto, additives, fillers, and polymeric materials, to increase the modulussuch that the resulting composition has a modulus as described above forthe high modulus HNP.

Relatively hard/high modulus HNP compositions may be blended with one ormore additional polymers, such as thermoplastic polymers and elastomers.Examples of thermoplastic polymers and elastomers suitable for blendinginclude those previously described as suitable for blending with therelatively soft/low modulus HNP compositions. In a particularembodiment, the relatively hard/high modulus HNP composition comprisesan acid copolymer and an additional polymer component, wherein theadditional polymer component is a non-acid polymer present in an amountof greater than 50 wt %, or an amount within a range having a lowerlimit of 50 or 55 or 60 or 65 or 70 and an upper limit of 80 or 85 or90, based on the combined weight of the acid copolymer and the non-acidpolymer. In another particular embodiment, the relatively hard/highmodulus HNP composition comprises an acid copolymer and an additionalpolymer component, wherein the additional polymer component is anon-acid polymer present in an amount of less than 50 wt %, or an amountwithin a range having a lower limit of 10 or 15 or 20 or 25 or 30 and anupper limit of 40 or 45 or 50, based on the combined weight of the acidcopolymer and the non-acid polymer

HNP compositions of the present invention, in the neat (i.e., unfilled)form, preferably have a specific gravity of from 0.95 g/cc to 0.99 g/cc.Any suitable filler, flake, fiber, particle, or the like, of an organicor inorganic material may be added to the HNP composition to increase ordecrease the specific gravity, particularly to adjust the weightdistribution within the golf ball, as further disclosed in U.S. Pat.Nos. 6,494,795, 6,547,677, 6,743,123, 7,074,137, and 6,688,991, theentire disclosures of which are hereby incorporated herein by reference.

In a particular embodiment, the relatively hard/high modulus HNPcomposition is formed by blending an acid polymer, a non-acid polymer, acation source, and a highly diverse mixture of organic acids.

In a particular aspect of this embodiment, the acid polymer is selectedfrom ethylene-acrylic acid and ethylene-methacrylic acid copolymers,optionally containing a softening monomer selected from n-butyl acrylateand iso-butyl acrylate. The acid polymer preferably has an acid contentwith a range having a lower limit of 2 or 10 or 15 or 16 mol % and anupper limit of 20 or 25 or 26 or 30 mol %. Examples of particularlysuitable commercially available acid polymers include, but are notlimited to, those given in Table 2 above.

In another particular aspect of this embodiment, the non-acid polymer isan elastomeric polymer. Suitable elastomeric polymers include, but arenot limited to:

(a) ethylene-alkyl acrylate polymers, particularly polyethylene-butylacrylate, polyethylene-methyl acrylate, and polyethylene-ethyl acrylate;

(b) metallocene-catalyzed polymers;

(c) ethylene-butyl acrylate-carbon monoxide polymers and ethylene-vinylacetate-carbon monoxide polymers;

(d) polyethylene-vinyl acetates;

(e) ethylene-alkyl acrylate polymers containing a cure site monomer;

(f) ethylene-propylene rubbers and ethylene-propylene-diene monomerrubbers;

(g) olefinic ethylene elastomers, particularly ethylene-octene polymers,ethylene-butene polymers, ethylene-propylene polymers, andethylene-hexene polymers;

(h) styrenic block copolymers;

(i) polyester elastomers;

(j) polyamide elastomers;

(k) polyolefin rubbers, particularly polybutadiene, polyisoprene, andstyrene-butadiene rubber; and

(l) thermoplastic polyurethanes.

Examples of particularly suitable commercially available non-acidpolymers include, but are not limited to, Lotader® ethylene-alkylacrylate polymers and Lotryl® ethylene-alkyl acrylate polymers, andparticularly Lotader® 4210, 4603, 4700, 4720, 6200, 8200, and AX8900commercially available from Arkema Corporation; Elvaloy® ACethylene-alkyl acrylate polymers, and particularly AC 1224, AC 1335, AC2116, AC3117, AC3427, and AC34035, commercially available from E. I. duPont de Nemours and Company; Fusabond® elastomeric polymers, such asethylene vinyl acetates, polyethylenes, metallocene-catalyzedpolyethylenes, ethylene propylene rubbers, and polypropylenes, andparticularly Fusabond® N525, C190, C250, A560, N416, N493, N614, P614,M603, E100, E158, E226, E265, E528, and E589, commercially availablefrom E. I. du Pont de Nemours and Company; Honeywell A-C polyethylenesand ethylene maleic anhydride copolymers, and particularly A-C 5180, A-C575, A-C 573, A-C 655, and A-C 395, commercially available fromHoneywell; Nordel® IP rubber, Elite® polyethylenes, Engage® elastomers,and Amplify® functional polymers, and particularly Amplify® GR 207, GR208, GR 209, GR 213, GR 216, GR 320, GR 380, and EA 100, commerciallyavailable from The Dow Chemical Company; Enable® metallocenepolyethylenes, Exact® plastomers, Vistamaxx® propylene-based elastomers,and Vistalon® EPDM rubber, commercially available from ExxonMobilChemical Company; Starflex® metallocene linear low density polyethylene,commercially available from LyondellBasell; Elvaloy® HP4051, HP441,HP661 and HP662 ethylene-butyl acrylate-carbon monoxide polymers andElvaloy® 741, 742 and 4924 ethylene-vinyl acetate-carbon monoxidepolymers, commercially available from E. I. du Pont de Nemours andCompany; Evatane® ethylene-vinyl acetate polymers having a vinyl acetatecontent of from 18 to 42%, commercially available from ArkemaCorporation; Elvax® ethylene-vinyl acetate polymers having a vinylacetate content of from 7.5 to 40%, commercially available from E. I. duPont de Nemours and Company; Vamac® G terpolymer of ethylene,methylacrylate and a cure site monomer, commercially available from E.I. du Pont de Nemours and Company; Vistalon® EPDM rubbers, commerciallyavailable from ExxonMobil Chemical Company; Kraton® styrenic blockcopolymers, and particularly Kraton® FG1901GT, FG1924GT, and RP6670GT,commercially available from Kraton Performance Polymers Inc.; Septon®styrenic block copolymers, commercially available from Kuraray Co.,Ltd.; Hytrel® polyester elastomers, and particularly Hytrel® 3078, 4069,and 556, commercially available from E. I. du Pont de Nemours andCompany; Riteflex® polyester elastomers, commercially available fromCelanese Corporation; Pebax® thermoplastic polyether block amides, andparticularly Pebax® 2533, 3533, 4033, and 5533, commercially availablefrom Arkema Inc.; Affinity® and Affinity® GA elastomers, Versify®ethylene-propylene copolymer elastomers, and Infuse® olefin blockcopolymers, commercially available from The Dow Chemical Company;Exxelor® polymer resins, and particularly Exxelor® PE 1040, PO 1015, PO1020, VA 1202, VA 1801, VA 1803, and VA 1840, commercially availablefrom ExxonMobil Chemical Company; and Royaltuf® EPDM, and particularlyRoyaltuf®498 maleic anhydride modified polyolefin based on an amorphousEPDM and Royaltuf®485 maleic anhydride modified polyolefin based on ansemi-crystalline EPDM, commercially available from Chemtura Corporation.

Additional examples of particularly suitable commercially availableelastomeric polymers include, but are not limited to, those given inTable 2 above.

The acid polymer and non-acid polymer are combined and reacted with acation source, such that at least 80% of all acid groups present areneutralized. The present invention is not meant to be limited by aparticular order for combining and reacting the acid polymer, non-acidpolymer and cation source. In a particular embodiment, the highlydiverse mixture of organic acids is used in an amount of from 10 wt % to60 wt %, or within a range having a lower limit of 10 or 20 or 30 or 40wt % and an upper limit of 40 or 50 or 60 wt %, based on the totalweight of the HNP composition. Suitable cation sources and fatty acidsand metal salts thereof are further disclosed above.

In another particular aspect of this embodiment, the acid polymer is anethylene-acrylic acid polymer having an acid content of 19 wt % orgreater, the non-acid polymer is a metallocene-catalyzed ethylene-butenecopolymer, optionally modified with maleic anhydride, the cation sourceis magnesium, and the highly diverse mixture of organic acids is presentin the composition in an amount of 20 to 50 wt %, based on the totalweight of the composition.

In the embodiments disclosed herein, the relatively soft/low modulus HNPcomposition and/or the relatively hard/high modulus HNP composition canbe either foamed or filled with density adjusting materials to providedesirable golf ball performance characteristics.

Golf balls having a layer formed from a relatively soft HNP compositionand a layer formed from a relatively hard HNP composition are furtherdisclosed, for example, in U.S. Patent Application Publication No.2007/0207880, the entire disclosure of which is hereby incorporatedherein by reference. Golf balls having a layer formed from a low modulusHNP composition and a layer formed from a high modulus HNP compositionare further disclosed, for example, in U.S. Pat. No. 7,211,008, theentire disclosure of which is hereby incorporated herein by reference.

Meanwhile, golf ball layers formed from a composition other than that ofthe at least one layer may be formed from any suitable golf ballcomposition such as a rubber composition or from a highly resilientthermoplastic polymer such as a conventional HNP composition.Particularly suitable thermoplastic polymers include Surlyn® ionomers,Hytrel® thermoplastic polyester elastomers, and ionomeric materials soldunder the trade names DuPont® HPF 1000, HPF 2000, HPF AD 1035, HPF AD1040, all of which are commercially available from E. I. du Pont deNemours and Company; Iotek® ionomers, commercially available fromExxonMobil Chemical Company; and Pebax® thermoplastic polyether blockamides, commercially available from Arkema Inc. Suitable rubber andthermoplastic polymer compositions are further disclosed below.

Suitable other layer materials for the golf balls disclosed hereininclude, but are not limited to, ionomer resin and blends thereof(particularly Surlyn® ionomer resin), polyurethanes, polyureas, castableor reaction injection moldable polyurethane, polyurea, or copolymer orhybrid of polyurethane/polyurea, (meth)acrylic acid, thermoplasticrubber polymers, polyethylene, and synthetic or natural vulcanizedrubber, such as balata. Suitable commercially available ionomericmaterials include, but are not limited to, Surlyn® ionomer resins andDuPont® HPF 1000, HPF 2000, HPF AD 1035, HPF AD 1040, commerciallyavailable from E. I. du Pont de Nemours and Company; and Iotek®ionomers, commercially available from ExxonMobil Chemical Company.

Particularly suitable layer materials include relatively softpolyurethanes and polyureas. When used as cover layer materials,polyurethanes and polyureas can be thermoset or thermoplastic. Thermosetmaterials can be formed into golf ball layers by conventional casting orreaction injection molding techniques. Thermoplastic materials can beformed into golf ball layers by conventional compression or injectionmolding techniques. Light stable polyureas and polyurethanes arepreferred for the outer cover layer material. Additional suitable coverand rubber core materials are disclosed, for example, in U.S. PatentApplication Publication No. 2005/0164810, U.S. Pat. No. 5,919,100, andPCT Publications WO00/23519 and WO00/29129, the entire disclosures ofwhich are hereby incorporated herein by reference. In embodiments of thepresent invention wherein a golf ball having a single layer cover isprovided, the cover layer material is preferably selected frompolyurethane and polyurea. In embodiments of the present inventionwherein a golf ball having a dual cover is provided, the inner coverlayer is preferably a high modulus thermoplastic, and the outer coverlayer is preferably selected from polyurethane and polyurea.

Suitable layer materials also include blends of ionomers withthermoplastic elastomers. Suitable ionomeric cover materials are furtherdisclosed, for example, in U.S. Pat. Nos. 6,653,382, 6,756,436,6,894,098, 6,919,393, and 6,953,820, the entire disclosures of which arehereby incorporated by reference. Suitable polyurethane cover materialsare further disclosed in U.S. Pat. Nos. 5,334,673, 6,506,851, 6,756,436,and 7,105,623, the entire disclosures of which are hereby incorporatedherein by reference. Suitable polyurea cover materials are furtherdisclosed in U.S. Pat. Nos. 5,484,870 and 6,835,794, the entiredisclosures of which are hereby incorporated herein by reference.Suitable polyurethane-urea hybrids are blends or copolymers comprisingurethane or urea segments as disclosed in U.S. Patent ApplicationPublication No. 2007/0117923, the entire disclosure of which is herebyincorporated herein by reference. Additional suitable cover materialsare disclosed, for example, in U.S. Patent Application Publication No.2005/0164810, U.S. Pat. No. 5,919,100, and PCT Publications WO00/23519and WO00/29129, the entire disclosures of which are hereby incorporatedherein by reference.

Ionomeric compositions may selected from:

-   -   (a) a composition comprising a “high acid ionomer” (i.e., having        an acid content of greater than 16 wt %), such as Surlyn 8150®,        a copolymer of ethylene and methacrylic acid, having an acid        content of 19 wt %, which is 45% neutralized with sodium,        commercially available from E. I. du Pont de Nemours and        Company;    -   (b) a composition comprising a high acid ionomer and a maleic        anhydride-grafted non-ionomeric polymer (e.g., Fusabond 572D®, a        maleic anhydride-grafted, metallocene-catalyzed ethylene-butene        copolymer having about 0.9 wt % maleic anhydride grafted onto        the copolymer, commercially available from E. I. du Pont de        Nemours and Company). A particularly preferred blend of high        acid ionomer and maleic anhydride-grafted polymer is a 84 wt        %/16 wt % blend of Surlyn 8150® and Fusabond 572D®. Blends of        high acid ionomers with maleic anhydride-grafted polymers are        further disclosed, for example, in U.S. Pat. Nos. 6,992,135 and        6,677,401, the entire disclosures of which are hereby        incorporated herein by reference;    -   (c) a composition comprising a 50/45/5 blend of Surlyn®        8940/Surlyn® 9650/Nucrel® 960, preferably having a material        hardness of from 80 to 85 Shore C;    -   (d) a composition comprising a 50/25/25 blend of Surlyn®        8940/Surlyn® 9650/Surlyn® 9910, preferably having a material        hardness of about 90 Shore C; and    -   (e) a composition comprising a 50/50 blend of Surlyn®        8940/Surlyn® 9650, preferably having a material hardness of        about 86 Shore C.

Surlyn® 8940 is an E/MAA copolymer in which the MAA acid groups havebeen partially neutralized with sodium ions. Surlyn® 9650 and Surlyn®9910 are two different grades of E/MAA copolymer in which the MAA acidgroups have been partially neutralized with zinc ions. Nucrel® 960 is anE/MAA copolymer resin nominally made with 15 wt % methacrylic acid.Surlyn® 8940, Surlyn® 9650, Surlyn® 9910, and Nucrel® 960 arecommercially available from E. I. du Pont de Nemours and Company.

Non-limiting examples layer materials are shown in the Examples below.

The material may include a flow modifier, such as, but not limited to,Nucrel® acid copolymer resins, and particularly Nucrel® 960. Nucrel®acid copolymer resins are commercially available from E. I. du Pont deNemours and Company.

Other layer compositions may comprise polyurethane, polyurea, or acopolymer or hybrid of polyurethane/polyurea. A layer material may bethermoplastic or thermoset.

In addition to the materials disclosed above, any of the core or coverlayers may comprise one or more of the following materials:thermoplastic elastomer, thermoset elastomer, synthetic rubber,thermoplastic vulcanizate, copolymeric ionomer, terpolymeric ionomer,polycarbonate, polyolefin, polyamide, copolymeric polyamide, polyesters,polyester-amides, polyether-amides, polyvinyl alcohols,acrylonitrile-butadiene-styrene copolymers, polyarylate, polyacrylate,polyphenylene ether, impact-modified polyphenylene ether, high impactpolystyrene, diallyl phthalate polymer, metallocene-catalyzed polymers,styrene-acrylonitrile (SAN), olefin-modified SAN,acrylonitrile-styrene-acrylonitrile, styrene-maleic anhydride (S/MA)polymer, styrenic copolymer, functionalized styrenic copolymer,functionalized styrenic terpolymer, styrenic terpolymer, cellulosepolymer, liquid crystal polymer (LCP), ethylene-propylene-diene rubber(EPDM), ethylene-vinyl acetate copolymer (EVA), ethylene propylenerubber (EPR), ethylene vinyl acetate, polyurea, and polysiloxane.Suitable polyamides for use as an additional material in compositionsdisclosed herein also include resins obtained by: (1) polycondensationof (a) a dicarboxylic acid, such as oxalic acid, adipic acid, sebacicacid, terephthalic acid, isophthalic acid or 1,4-cyclohexanedicarboxylicacid, with (b) a diamine, such as ethylenediamine,tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, ordecamethylenediamine, 1,4-cyclohexyldiamine or m-xylylenediamine; (2) aring-opening polymerization of cyclic lactam, such as ε-caprolactam orω-laurolactam; (3) polycondensation of an aminocarboxylic acid, such as6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid or12-aminododecanoic acid; or (4) copolymerzation of a cyclic lactam witha dicarboxylic acid and a diamine. Specific examples of suitablepolyamides include Nylon 6, Nylon 66, Nylon 610, Nylon 11, Nylon 12,copolymerized Nylon, Nylon MXD6, and Nylon 46.

In embodiments wherein at least one layer is formed from a rubbercomposition, suitable rubber compositions include natural and syntheticrubbers, including, but not limited to, polybutadiene, polyisoprene,ethylene propylene rubber (“EPR”), ethylene propylene diene rubber(“EPDM”), styrenic block copolymer rubbers (such as SI, SIS, SB, SBS,SIBS, and the like, where “S” is styrene, “I” is isobutylene, and “B” isbutadiene), butyl rubber, halobutyl rubber, copolymers of isobutyleneand para-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene, copolymers of butadiene with acrylonitrile,polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber,acrylonitrile chlorinated isoprene rubber, and combinations of two ormore thereof. Diene rubbers are preferred, particularly polybutadienesand mixtures of polybutadiene with other elastomers, and especially1,4-polybutadiene having a cis-structure of at least 40%. In aparticularly preferred embodiment, the rubber composition is a reactionproduct of a diene rubber, a crosslinking agent, a filler, aco-crosslinking agent or free radical initiator, and optionally acis-to-trans catalyst. The rubber is preferably selected frompolybutadiene and styrene-butadiene. The crosslinking agent typicallyincludes a metal salt, such as a zinc-, aluminum-, sodium-, lithium-,nickel-, calcium-, or magnesium salt, of an unsaturated fatty acid ormonocarboxylic acid, such as (meth) acrylic acid. Preferred crosslinkingagents include zinc acrylate, zinc diacrylate (ZDA), zinc methacrylate,and zinc dimethacrylate (ZDMA), and mixtures thereof. The crosslinkingagent is present in an amount sufficient to crosslink a portion of thechains of the polymers in the composition. The crosslinking agent isgenerally present in the rubber composition in an amount of from 15 to30 phr, or from 19 to 25 phr, or from 20 to 24 phr. The desiredcompression may be obtained by adjusting the amount of crosslinking,which can be achieved, for example, by altering the type and amount ofcrosslinking agent. The free radical initiator can be any knownpolymerization initiator which decomposes during the cure cycle,including, but not limited to, dicumyl peroxide, 1,1-di-(t-butylperoxy)3,3,5-trimethyl cyclohexane, a-a bis-(t-butylperoxy) diisopropylbenzene,2,5-dimethyl-2,5 di-(t-butylperoxy) hexane or di-t-butyl peroxide, andmixtures thereof. The rubber composition optionally contains one or moreantioxidants. Antioxidants are compounds that can inhibit or prevent theoxidative degradation of the rubber. Suitable antioxidants include, forexample, dihydroquinoline antioxidants, amine type antioxidants, andphenolic type antioxidants. The rubber composition may also contain oneor more fillers to adjust the density and/or specific gravity of thecore or cover. Fillers are typically polymeric or mineral particles.Exemplary fillers include precipitated hydrated silica, clay, talc,asbestos, glass fibers, aramid fibers, mica, calcium metasilicate,barium sulfate, zinc sulfide, lithopone, silicates, silicon carbide,diatomaceous earth, polyvinyl chloride, carbonates (e.g., calciumcarbonate and magnesium carbonate), metals (e.g., titanium, tungsten,aluminum, bismuth, nickel, molybdenum, iron, lead, copper, boron,cobalt, beryllium, zinc, and tin), metal alloys (e.g., steel, brass,bronze, boron carbide whiskers, and tungsten carbide whiskers), metaloxides (e.g., zinc oxide, iron oxide, aluminum oxide, titanium oxide,magnesium oxide, and zirconium oxide), particulate carbonaceousmaterials (e.g., graphite, carbon black, cotton flock, natural bitumen,cellulose flock, and leather fiber), microballoons (e.g., glass andceramic), fly ash, regrind, nanofillers and combinations thereof. Therubber composition may also contain one or more additives selected fromfree radical scavengers, accelerators, scorch retarders, coloringagents, fluorescent agents, chemical blowing and foaming agents,defoaming agents, stabilizers, softening agents, impact modifiers,plasticizers, and the like. The rubber composition may also contain asoft and fast agent, such as those disclosed in U.S. patent applicationSer. No. 11/972,240, the entire disclosure of which is herebyincorporated herein by reference. Examples of commercially availablepolybutadienes suitable for use in forming golf ball layers include, butare not limited to, Buna CB23, commercially available from LANXESSCorporation; SE BR-1220, commercially available from The Dow ChemicalCompany; Europrene® NEOCIS® BR 40 and BR 60, commercially available fromPolimeri Europa; UBEPOL-BR® rubbers, commercially available from UBEIndustries, Ltd.; and BR 01 commercially available from Japan SyntheticRubber Co., Ltd. Suitable types and amounts of rubber, crosslinkingagent, filler, co-crosslinking agent, initiator and additives are morefully described in, for example, U.S. Patent Application Publication No.2004/0214661, 2003/0144087, and 2003/0225197, and U.S. Pat. Nos.6,566,483, 6,695,718, and 6,939,907, the entire disclosures of which arehereby incorporated herein by reference.

In embodiments wherein at least one layer is formed from a conventionalHNP composition, suitable HNP compositions comprise an HNP andoptionally additives, fillers, and/or melt flow modifiers. Suitable HNPsare salts of homopolymers and copolymers of α,β-ethylenicallyunsaturated mono- or dicarboxylic acids, and combinations thereof,optionally including a softening monomer. The acid polymer isneutralized to 70% or higher, including up to 100%, with a suitablecation source. Suitable additives and fillers include, for example,blowing and foaming agents, optical brighteners, coloring agents,fluorescent agents, whitening agents, UV absorbers, light stabilizers,defoaming agents, processing aids, mica, talc, nanofillers,antioxidants, stabilizers, softening agents, fragrance components,plasticizers, impact modifiers, acid copolymer wax, surfactants;inorganic fillers, such as zinc oxide, titanium dioxide, tin oxide,calcium oxide, magnesium oxide, barium sulfate, zinc sulfate, calciumcarbonate, zinc carbonate, barium carbonate, mica, talc, clay, silica,lead silicate, and the like; high specific gravity metal powder fillers,such as tungsten powder, molybdenum powder, and the like; regrind, i.e.,core material that is ground and recycled; and nano-fillers. Suitablemelt flow modifiers include, for example, fatty acids and salts thereof,polyamides, polyesters, polyacrylates, polyurethanes, polyethers,polyureas, polyhydric alcohols, and combinations thereof. Suitable HNPcompositions also include blends of HNPs with partially neutralizedionomers as disclosed, for example, in U.S. Patent ApplicationPublication No. 2006/0128904, the entire disclosure of which is herebyincorporated herein by reference, and blends of HNPs with additionalthermoplastic and thermoset materials, including, but not limited to,ionomers, acid copolymers, engineering thermoplastics, fattyacid/salt-based highly neutralized polymers, polybutadienes,polyurethanes, polyesters, thermoplastic elastomers, and otherconventional polymeric materials. Suitable HNP compositions are furtherdisclosed, for example, in U.S. Pat. Nos. 6,653,382, 6,756,436,6,777,472, 6,894,098, 6,919,393, and 6,953,820, the entire disclosuresof which are hereby incorporated herein by reference.

Other preferred materials suitable for use as an additional material ingolf ball compositions disclosed herein include Skypel polyesterelastomers, commercially available from SK Chemicals of South Korea;Septon® diblock and triblock copolymers, commercially available fromKuraray Corporation of Kurashiki, Japan; and Kraton® diblock andtriblock copolymers, commercially available from Kraton Polymers LLC ofHouston, Tex.

Conventional ionomers are also well suited for blending withcompositions disclosed herein. Suitable ionomeric polymers includeα-olefin/unsaturated carboxylic acid copolymer- or terpolymer-typeionomeric resins. Copolymeric ionomers are obtained by neutralizing atleast a portion of the carboxylic groups in a copolymer of an α-olefinand an α,β-unsaturated carboxylic acid having from 3 to 8 carbon atoms,with a metal ion. Terpolymeric ionomers are obtained by neutralizing atleast a portion of the carboxylic groups in a terpolymer of an α-olefin,an α,β-unsaturated carboxylic acid having from 3 to 8 carbon atoms, andan α,β-unsaturated carboxylate having from 2 to 22 carbon atoms, with ametal ion. Examples of suitable α-olefins for copolymeric andterpolymeric ionomers include ethylene, propylene, 1-butene, and1-hexene. Examples of suitable unsaturated carboxylic acids forcopolymeric and terpolymeric ionomers include acrylic, methacrylic,ethacrylic, α-chloroacrylic, crotonic, maleic, fumaric, and itaconicacid. Copolymeric and terpolymeric ionomers include ionomers havingvaried acid contents and degrees of acid neutralization, neutralized bymonovalent or bivalent cations as disclosed herein. Examples ofcommercially available ionomers suitable for blending with compositionsdisclosed herein include Surlyn® ionomer resins, commercially availablefrom E. I. du Pont de Nemours and Company, and Iotek® ionomers,commercially available from ExxonMobil Chemical Company.

Silicone materials are also well suited for blending with compositionsdisclosed herein. Suitable silicone materials include monomers,oligomers, prepolymers, and polymers, with or without adding reinforcingfiller. One type of silicone material that is suitable can incorporateat least 1 alkenyl group having at least 2 carbon atoms in theirmolecules. Examples of these alkenyl groups include, but are not limitedto, vinyl, allyl, butenyl, pentenyl, hexenyl, and decenyl. The alkenylfunctionality can be located at any location of the silicone structure,including one or both terminals of the structure. The remaining (i.e.,non-alkenyl) silicon-bonded organic groups in this component areindependently selected from hydrocarbon or halogenated hydrocarbongroups that contain no aliphatic unsaturation. Non-limiting examples ofthese include: alkyl groups, such as methyl, ethyl, propyl, butyl,pentyl, and hexyl; cycloalkyl groups, such as cyclohexyl andcycloheptyl; aryl groups, such as phenyl, tolyl, and xylyl; aralkylgroups, such as benzyl and phenethyl; and halogenated alkyl groups, suchas 3,3,3-trifluoropropyl and chloromethyl. Another type of suitablesilicone material is one having hydrocarbon groups that lack aliphaticunsaturation. Specific examples include: trimethylsiloxy-endblockeddimethylsiloxane-methylhexenylsiloxane copolymers;dimethylhexenylsiloxy-endblocked dimethylsiloxane-methylhexenylsiloxanecopolymers; trimethylsiloxy-endblockeddimethylsiloxane-methylvinylsiloxane copolymers;trimethylsiloxyl-endblockedmethylphenylsiloxane-dimethylsiloxane-methylvinysiloxane copolymers;dimethylvinylsiloxy-endblocked dimethylpolysiloxanes;dimethylvinylsiloxy-endblocked dimethylsiloxane-methylvinylsiloxanecopolymers; dimethylvinylsiloxy-endblocked methylphenylpolysiloxanes;dimethylvinylsiloxy-endblockedmethylphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers;and the copolymers listed above wherein at least one group isdimethylhydroxysiloxy. Examples of commercially available siliconessuitable for blending with compositions disclosed herein includeSilastic® silicone rubber, commercially available from Dow CorningCorporation of Midland, Mich.; Blensil® silicone rubber, commerciallyavailable from General Electric Company of Waterford, N.Y.; andElastosil® silicones, commercially available from Wacker Chemie AG ofGermany.

Other types of copolymers can also be added to the golf ballcompositions disclosed herein. For example, suitable copolymerscomprising epoxy monomers include styrene-butadiene-styrene blockcopolymers in which the polybutadiene block contains an epoxy group, andstyrene-isoprene-styrene block copolymers in which the polyisopreneblock contains epoxy. Examples of commercially available epoxyfunctionalized copolymers include ESBS A1005, ESBS A1010, ESBS A1020,ESBS AT018, and ESBS AT019 epoxidized styrene-butadiene-styrene blockcopolymers, commercially available from Daicel Chemical Industries, Ltd.of Japan.

Ionomeric compositions used to form golf ball layers of the presentinvention can be blended with non-ionic thermoplastic resins,particularly to manipulate product properties. Examples of suitablenon-ionic thermoplastic resins include, but are not limited to,polyurethane, poly-ether-ester, poly-amide-ether, polyether-urea, Pebax®thermoplastic polyether block amides commercially available from ArkemaInc., styrene-butadiene-styrene block copolymers,styrene(ethylene-butylene)-styrene block copolymers, polyamides,polyesters, polyolefins (e.g., polyethylene, polypropylene,ethylene-propylene copolymers, ethylene-(meth)acrylate,ethylene-(meth)acrylic acid, functionalized polymers with maleicanhydride grafting, epoxidation, etc., elastomers (e.g., EPDM,metallocene-catalyzed polyethylene) and ground powders of the thermosetelastomers.

Also suitable are compositions having high COR when formed into solidspheres disclosed in U.S. Patent Application Publication No.2003/0130434 and U.S. Pat. No. 6,653,382, the entire disclosures ofwhich are hereby incorporated herein by reference. Reference is alsomade to U.S. Patent Application Publication No. 2003/0144087 for variousball constructions and materials that can be used in golf ball core,intermediate, and cover layers.

Additional materials suitable for forming layers include thecompositions disclosed in U.S. Pat. No. 7,300,364, the entire disclosureof which is hereby incorporated herein by reference. For example,suitable core materials include HNPs neutralized with organic fattyacids and salts thereof, metal cations, or a combination of both. Inaddition to HNPs neutralized with organic fatty acids and salts thereof,core compositions may comprise at least one rubber material having aresilience index of at least about 40. Preferably the resilience indexis at least about 50. Polymers that produce resilient golf balls and,therefore, are suitable for the present invention, include but are notlimited to CB23, CB22, commercially available from of Bayer Corp. ofOrange, Tex., BR60, commercially available from Enichem of Italy, and1207G, commercially available from Goodyear Corp. of Akron, Ohio.Additionally, the unvulcanized rubber, such as polybutadiene, in golfballs prepared according to the invention typically has a Mooneyviscosity of between about 40 and about 80, more preferably, betweenabout 45 and about 65, and most preferably, between about 45 and about55. Mooney viscosity is typically measured according to ASTM-D1646.

In addition to the above materials, layers can be formed from a lowdeformation material selected from metal, rigid plastics, polymersreinforced with high strength organic or inorganic fillers or fibers,and blends and composites thereof. Suitable low deformation materialsalso include those disclosed in U.S. Patent Application Publication No.2005/0250600, the entire disclosure of which is hereby incorporatedherein by reference.

EXAMPLES

It should be understood that the examples below are for illustrativepurposes only. In no manner is the present invention limited to thespecific disclosures herein.

Additional Examples of Suitable HNPs

The HNPs of Table 5 below have been found to be particularly useful asthe relatively soft/low modulus HNP and/or the relatively hard/highmodulus HNP of the present invention.

TABLE 5 Flexural Hardness**, Hardness**, cation Modulus*, Shore C ShoreD Example source psi (18 day) (annealed) 1 Ca/Mg 71,600 88 57 2 Ca/Li70,300 89 58 3 Ca 70,100 92 60 4 Ca/Zn 60,400 88 58 5 Mg 38,300 84 52 6Mg 27,600 84 52 7 Mg 16,300 78 45 8 Mg 10,600 70 40 9 Mg 10,400 69 39*Flexural modulus was measured according to ASTM D790-03 Procedure B.**Hardness was measured according to ASTM D2240.

Examples 6-9 are particularly suitable for use as the relatively softHNP composition. Examples 5-9 are particularly suitable for use as therelatively soft HNP composition. Examples 1-6 are particularly suitablefor use as the relatively hard HNP composition. Examples 1-4 areparticularly suitable for use as the relatively hard HNP composition.Examples 6-9 are particularly suitable for use as the low modulus HNPcomposition. Examples 5-9 are particularly suitable for use as the lowmodulus HNP composition. Examples 1-6 are particularly suitable for useas the high modulus HNP composition. Examples 1-4 are particularlysuitable for use as the high modulus HNP composition.

Additional Examples of Suitable Ionomeric Cover Layer Compositions

Twelve ionomeric inner cover layer compositions according to the presentinvention were prepared by melt blending Surlyn® 8150 and Fusabond® 572Din a twin screw extruder, at a temperature of at least 450° F. (230°C.). The relative amounts of each component used are indicated in Table4 below.

Flex bars of each blend composition were formed and evaluated forhardness according to ASTM D2240 following 10 days of aging at 50%relative humidity and 23° C. The results are reported in Table 6 below.

TABLE 6 Fusabond ® Shore C Surlyn ® 8150, 572D, Hardness at Example wt %wt % 10 Days 1 89 11 91.2 2 84 16 89.8 3 84 16 90.4 4 84 16 89.6 5 81 1988.9 6 80 20 89.1 7 78 22 88.1 8 76 24 87.6 9 76 24 87.2 10 73 27 86.611 71 29 86.7 12 67 33 84.0

The following commercially available materials were used in the belowexamples:

-   -   A-C® 5120 ethylene acrylic acid copolymer with an acrylic acid        content of 15%,    -   A-C® 5180 ethylene acrylic acid copolymer with an acrylic acid        content of 20%,    -   A-C® 395 high density oxidized polyethylene homopolymer, and    -   A-C® 575 ethylene maleic anhydride copolymer, commercially        available from Honeywell;    -   CB23 high-cis neodymium-catalyzed polybutadiene rubber,        commercially available from Lanxess Corporation;    -   CA1700 Soya fatty acid, CA1726 linoleic acid, and CA1725        conjugated linoleic acid, commercially available from Chemical        Associates;    -   Century® 1107 highly purified isostearic acid mixture of        branched and straight-chain C18 fatty acid, commercially        available from Arizona Chemical;    -   Clarix® 011370-01 ethylene acrylic acid copolymer with an        acrylic acid content of 13% and    -   Clarix® 011536-01 ethylene acrylic acid copolymer with an        acrylic acid content of 15%, commercially available from A.        Schulman Inc.;    -   Elvaloy® AC 1224 ethylene-methyl acrylate copolymer with a        methyl acrylate content of 24 wt %,    -   Elvaloy® AC 1335 ethylene-methyl acrylate copolymer with a        methyl acrylate content of 35 wt %,    -   Elvaloy® AC 2116 ethylene-ethyl acrylate copolymer with an ethyl        acrylate content of 16 wt %,    -   Elvaloy® AC 3427 ethylene-butyl acrylate copolymer having a        butyl acrylate content of 27 wt %, and    -   Elvaloy® AC 34035 ethylene-butyl acrylate copolymer having a        butyl acrylate content of 35 wt %, commercially available        from E. I. du Pont de Nemours and Company;    -   Escor® AT-320 ethylene acid terpolymer, commercially available        from ExxonMobil Chemical Company;    -   Exxelor® VA 1803 amorphous ethylene copolymer functionalized        with maleic anhydride, commercially available from ExxonMobil        Chemical Company;    -   Fusabond® N525 metallocene-catalyzed polyethylene,    -   Fusabond® N416 chemically modified ethylene elastomer,    -   Fusabond® C190 anhydride modified ethylene vinyl acetate        copolymer, and    -   Fusabond® P614 functionalized polypropylene, commercially        available from E. I. du Pont de Nemours and Company;    -   Hytrel® 3078 very low modulus thermoplastic polyester elastomer,        commercially available from E. I. du Pont de Nemours and        Company;    -   Kraton® FG 1901 GT linear triblock copolymer based on styrene        and ethylene/butylene with a polystyrene content of 30% and    -   Kraton® FG1924GT linear triblock copolymer based on styrene and        ethylene/butylene with a polystyrene content of 13%,        commercially available from Kraton Performance Polymers Inc.;    -   Lotader® 4603, 4700 and 4720, random copolymers of ethylene,        acrylic ester and maleic anhydride, commercially available from        Arkema Corporation;    -   Nordel® IP 4770 high molecular weight semi-crystalline EPDM        rubber, commercially available from The Dow Chemical Company;    -   Nucrel® 9-1, Nucrel® 599, Nucrel® 960, Nucrel® 0407, Nucrel®        0609, Nucrel® 1214, Nucrel® 2906, Nucrel® 2940, Nucrel® 30707,        Nucrel® 31001, and Nucrel® AE acid copolymers, commercially        available from E. I. du Pont de Nemours and Company;    -   Primacor® 3150, 3330, 59801, and 59901 acid copolymers,        commercially available from The Dow Chemical Company;    -   Royaltuf® 498 maleic anhydride modified polyolefin based on an        amorphous EPDM, commercially available from Chemtura        Corporation;    -   Sylfat® FA2 tall oil fatty acid, commercially available from        Arizona Chemical;    -   Vamac® G terpolymer of ethylene, methylacrylate and a cure site        monomer, commercially available from E. I. du Pont de Nemours        and Company; and    -   XUS 60758.08L ethylene acrylic acid copolymer with an acrylic        acid content of 13.5%, commercially available from The Dow        Chemical Company.

Various compositions were melt blended using components as given inTable 5 below. The compositions were neutralized by adding a cationsource in an amount sufficient to neutralize, theoretically, 110% of theacid groups present in components 1 and 3, except for example 72, inwhich the cation source was added in an amount sufficient to neutralize75% of the acid groups. Magnesium hydroxide was used as the cationsource, except for example 68, in which magnesium hydroxide and sodiumhydroxide were used in an equivalent ratio of 4:1. In addition tocomponents 1-3 and the cation source, example 71 contains ethyl oleateplasticizer.

The relative amounts of component 1 and component 2 used are indicatedin Table 7 below, and are reported in wt %, based on the combined weightof components 1 and 2. The relative amounts of component 3 used areindicated in Table 7 below, and are reported in wt %, based on the totalweight of the composition.

TABLE 7 Example Component 1 wt % Component 2 wt % Component 3 wt % 1Primacor 5980I 78 Lotader 4603 22 magnesium oleate 41.6 2 Primacor 5980I84 Elvaloy AC 1335 16 magnesium oleate 41.6 3 Primacor 5980I 78 ElvaloyAC 3427 22 magnesium oleate 41.6 4 Primacor 5980I 78 Elvaloy AC 1335 22magnesium oleate 41.6 5 Primacor 5980I 78 Elvaloy AC 1224 22 magnesiumoleate 41.6 6 Primacor 5980I 78 Lotader 4720 22 magnesium oleate 41.6 7Primacor 5980I 85 Vamac G 15 magnesium oleate 41.6 8 Primacor 5980I 90Vamac G 10 magnesium oleate 41.6 8.1 Primacor 5990I 90 Fusabond 614 10magnesium oleate 41.6 9 Primacor 5980I 78 Vamac G 22 magnesium oleate41.6 10 Primacor 5980I 75 Lotader 4720 25 magnesium oleate 41.6 11Primacor 5980I 55 Elvaloy AC 3427 45 magnesium oleate 41.6 12 Primacor5980I 55 Elvaloy AC 1335 45 magnesium oleate 41.6 12.1 Primacor 5980I 55Elvaloy AC 34035 45 magnesium oleate 41.6 13 Primacor 5980I 55 ElvaloyAC 2116 45 magnesium oleate 41.6 14 Primacor 5980I 78 Elvaloy AC 3403522 magnesium oleate 41.6 14.1 Primacor 5990I 80 Elvaloy AC 34035 20magnesium oleate 41.6 15 Primacor 5980I 34 Elvaloy AC 34035 66 magnesiumoleate 41.6 16 Primacor 5980I 58 Vamac G 42 magnesium oleate 41.6 17Primacor 5990I 80 Fusabond 416 20 magnesium oleate 41.6 18 Primacor5980I 100 — — magnesium oleate 41.6 19 Primacor 5980I 78 Fusabond 416 22magnesium oleate 41.6 20 Primacor 5990I 100 — — magnesium oleate 41.6 21Primacor 5990I 20 Fusabond 416 80 magnesium oleate 41.6 21.1 Primacor5990I 20 Fusabond 416 80 magnesium oleate 31.2 21.2 Primacor 5990I 20Fusabond 416 80 magnesium oleate 20.8 22 Clarix 011370 30.7 Fusabond 41669.3 magnesium oleate 41.6 23 Primacor 5990I 20 Royaltuf 498 80magnesium oleate 41.6 24 Primacor 5990I 80 Royaltuf 498 20 magnesiumoleate 41.6 25 Primacor 5990I 80 Kraton 20 magnesium oleate 41.6FG1924GT 26 Primacor 5990I 20 Kraton 80 magnesium oleate 41.6 FG1924GT27 Nucrel 30707 57 Fusabond 416 43 magnesium oleate 41.6 28 Primacor5990I 80 Hytrel 3078 20 magnesium oleate 41.6 29 Primacor 5990I 20Hytrel 3078 80 magnesium oleate 41.6 30 Primacor 5980I 26.8 Elvaloy AC34035 73.2 magnesium oleate 41.6 31 Primacor 5980I 26.8 Lotader 460373.2 magnesium oleate 41.6 32 Primacor 5980I 26.8 Elvaloy AC 2116 73.2magnesium oleate 41.6 33 Escor AT-320 30 Elvaloy AC 34035 52 magnesiumoleate 41.6 Primacor 5980I 18 34 Nucrel 30707 78.5 Elvaloy AC 34035 21.5magnesium oleate 41.6 35 Nucrel 30707 78.5 Fusabond 416 21.5 magnesiumoleate 41.6 36 Primacor 5980I 26.8 Fusabond 416 73.2 magnesium oleate41.6 37 Primacor 5980I 19.5 Fusabond N525 80.5 magnesium oleate 41.6 38Clarix 011536- 26.5 Fusabond N525 73.5 magnesium oleate 41.6 01 39Clarix 011370- 31 Fusabond N525 69 magnesium oleate 41.6 01 39.1 XUS60758.08L 29.5 Fusabond N525 70.5 magnesium oleate 41.6 40 Nucrel 3100142.5 Fusabond N525 57.5 magnesium oleate 41.6 41 Nucrel 30707 57.5Fusabond N525 42.5 magnesium oleate 41.6 42 Escor AT-320 66.5 FusabondN525 33.5 magnesium oleate 41.6 43 Nucrel 21 Fusabond N525 79 magnesiumoleate 41.6 2906/2940 44 Nucrel 960 26.5 Fusabond N525 73.5 magnesiumoleate 41.6 45 Nucrel 1214 33 Fusabond N525 67 magnesium oleate 41.6 46Nucrel 599 40 Fusabond N525 60 magnesium oleate 41.6 47 Nucrel 9-1 44.5Fusabond N525 55.5 magnesium oleate 41.6 48 Nucrel 0609 67 Fusabond N52533 magnesium oleate 41.6 49 Nucrel 0407 100 — — magnesium oleate 41.6 50Primacor 5980I 90 Fusabond N525 10 magnesium oleate 41.6 51 Primacor5980I 80 Fusabond N525 20 magnesium oleate 41.6 52 Primacor 5980I 70Fusabond N525 30 magnesium oleate 41.6 53 Primacor 5980I 60 FusabondN525 40 magnesium oleate 41.6 54 Primacor 5980I 50 Fusabond N525 50magnesium oleate 41.6 55 Primacor 5980I 40 Fusabond N525 60 magnesiumoleate 41.6 56 Primacor 5980I 30 Fusabond N525 70 magnesium oleate 41.657 Primacor 5980I 20 Fusabond N525 80 magnesium oleate 41.6 58 Primacor5980I 10 Fusabond N525 90 magnesium oleate 41.6 59 — — Fusabond N525 100magnesium oleate 41.6 60 Nucrel 0609 40 Fusabond N525 20 magnesiumoleate 41.6 Nucrel 0407 40 61 Nucrel AE 100 — — magnesium oleate 41.6 62Primacor 5980I 30 Fusabond N525 70 CA1700 soya fatty 41.6 acid magnesiumsalt 63 Primacor 5980I 30 Fusabond N525 70 CA1726 linoleic acid 41.6magnesium salt 64 Primacor 5980I 30 Fusabond N525 70 CA1725 41.6conjugated linoleic acid magnesium salt 65 Primacor 5980I 30 FusabondN525 70 Century 1107 41.6 isostearic acid magnesium salt 66 A-C 512073.3 Lotader 4700 26.7 oleic acid 41.6 magnesium salt 67 A-C 5120 73.3Elvaloy 34035 26.7 oleic acid 41.6 magnesium salt 68 Primacor 5980I 78.3Lotader 4700 21.7 oleic acid 41.6 magnesium salt and sodium salt 69Primacor 5980I 47 Elvaloy AC34035 13 — — A-C 5180 40 70 Primacor 5980I30 Fusabond N525 70 Sylfat FA2 41.6 magnesium salt 71 Primacor 5980I 30Fusabond N525 70 oleic acid magnesium salt 31.2 ethyl oleate 10 72Primacor 5980I 80 Fusabond N525 20 sebacic acid 41.6 magnesium salt 73Primacor 5980I 60 — — — — A-C 5180 40 74 Primacor 5980I 78.3 — — oleicacid 41.6 A-C 575 21.7 magnesium salt 75 Primacor 5980I 78.3 Exxelor VA1803 21.7 oleic acid 41.6 magnesium salt 76 Primacor 5980I 78.3 A-C 39521.7 oleic acid 41.6 magnesium salt 77 Primacor 5980I 78.3 Fusabond C19021.7 oleic acid 41.6 magnesium salt 78 Primacor 5980I 30 Kraton FG 190170 oleic acid 41.6 magnesium salt 79 Primacor 5980I 30 Royaltuf 498 70oleic acid 41.6 magnesium salt 80 A-C 5120 40 Fusabond N525 60 oleicacid 41.6 magnesium salt 81 Primacor 5980I 30 Fusabond N525 70 erucicacid 41.6 magnesium salt 82 Primacor 5980I 30 CB23 70 oleic acid 41.6magnesium salt 83 Primacor 5980I 30 Nordel IP 4770 70 oleic acid 41.6magnesium salt 84 Primacor 5980I 48 Fusabond N525 20 oleic acid 41.6 A-C5180 32 magnesium salt 85 Nucrel 2806 22.2 Fusabond N525 77.8 oleic acid41.6 magnesium salt 86 Primacor 3330 61.5 Fusabond N525 38.5 oleic acid41.6 magnesium salt 87 Primacor 3330 45.5 Fusabond N525 20 oleic acid41.6 Primacor 3150 34.5 magnesium salt 88 Primacor 3330 28.5 — — oleicacid 41.6 Primacor 3150 71.5 magnesium salt 89 Primacor 3150 67 FusabondN525 33 oleic acid 41.6 magnesium salt 90 Primacor 5980I 55 Elvaloy AC34035 45 oleic acid magnesium salt 31.2 ethyl oleate 10

Solid spheres of each composition were injection molded, and the solidsphere COR, compression, Shore D hardness, and Shore C hardness of theresulting spheres were measured after two weeks. The results arereported in Table 8 below. The surface hardness of a sphere is obtainedfrom the average of a number of measurements taken from opposinghemispheres, taking care to avoid making measurements on the partingline of the sphere or on surface defects, such as holes or protrusions.Hardness measurements are made pursuant to ASTM D-2240 “IndentationHardness of Rubber and Plastic by Means of a Durometer.” Because of thecurved surface, care must be taken to insure that the sphere is centeredunder the durometer indentor before a surface hardness reading isobtained. A calibrated, digital durometer, capable of reading to 0.1hardness units is used for all hardness measurements and is set torecord the maximum hardness reading obtained for each measurement. Thedigital durometer must be attached to, and its foot made parallel to,the base of an automatic stand. The weight on the durometer and attackrate conform to ASTM D-2240.

TABLE 8 Solid Solid Solid Sphere Solid Sphere Sphere Sphere Ex. CORCompression Shore D Shore C 1 0.845 120 59.6 89.2 2 * * * * 3 0.871 11757.7 88.6 4 0.867 122 63.7 90.6 5 0.866 119 62.8 89.9 6 * * * *7 * * * * 8 * * * * 8.1 0.869 127 65.3 92.9 9 * * * * 10 * * * *11 * * * * 12 0.856 101 55.7 82.4 12.1 0.857 105 53.2 81.3 13 * * * * 140.873 122 64.0 91.1 14.1 * * * * 15 * * * * 16 * * * * 17 0.878 117 60.189.4 18 0.853 135 67.6 94.9 19 * * * * 20 0.857 131 66.2 94.4 21 0.75226 34.8 57.1 21.1 0.729 9 34.3 56.3 21.2 0.720 2 33.8 55.2 22 * * * *23 * * * * 24 * * * * 25 * * * * 26 * * * * 27 * * * * 28 * * * *29 * * * * 30 ** 66 42.7 65.5 31 0.730 67 45.6 68.8 32 ** 100 52.4 78.233 0.760 64 43.6 64.5 34 0.814 91 52.8 80.4 35 * * * * 36 * * * *37 * * * * 38 * * * * 39 * * * * 39.1 * * * * 40 * * * * 41 * * * *42 * * * * 43 * * * * 44 * * * * 45 * * * * 46 * * * * 47 * * * *48 * * * * 49 * * * * 50 * * * * 51 0.873 121 61.5 90.2 52 0.870 11660.4 88.2 53 0.865 107 57.7 84.4 54 0.853 97 53.9 80.2 55 0.837 82 50.175.5 56 0.818 66 45.6 70.7 57 0.787 45 41.3 64.7 58 0.768 26 35.9 57.359 * * * * 60 * * * * 61 * * * * 62 * * * * 63 * * * * 64 * * * *65 * * * * 66 * * * * 67 * * * * 68 * * * * 69 * * * * 70 * * * *71 * * * * 72 * * * * 73 * * * * 74 * * * * 75 * * * * 76 * * * *77 * * * * 78 * * * * 79 * * * * 80 * * * * 81 * * * * 82 * * * *83 * * * * 84 * * * * 85 * * * * 86 * * * * 87 * * * * 88 * * * *89 * * * * 90 * * * * * not measured ** sphere broke during measurement

When numerical lower limits and numerical upper limits are set forthherein, it is contemplated that any combination of these values may beused.

All patents, publications, test procedures, and other references citedherein, including priority documents, are fully incorporated byreference to the extent such disclosure is not inconsistent with thisinvention and for all jurisdictions in which such incorporation ispermitted.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by those ofordinary skill in the art without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the scope of theclaims appended hereto be limited to the examples and descriptions setforth herein, but rather that the claims be construed as encompassingall of the features of patentable novelty which reside in the presentinvention, including all features which would be treated as equivalentsthereof by those of ordinary skill in the art to which the inventionpertains.

The present invention is not limited by any particular process forforming the golf ball layer(s). It should be understood that thelayer(s) can be formed by any suitable technique, including injectionmolding, compression molding, casting, and reaction injection molding.

When injection molding is used, the composition is typically in apelletized or granulated form that can be easily fed into the throat ofan injection molding machine wherein it is melted and conveyed via ascrew in a heated barrel at temperatures of from 150° F. to 600° F.,preferably from 200° F. to 500° F. The molten composition is ultimatelyinjected into a closed mold cavity, which may be cooled, at ambient orat an elevated temperature, but typically the mold is cooled to atemperature of from 50° F. to 70° F. After residing in the closed moldfor a time of from 1 second to 300 seconds, preferably from 20 secondsto 120 seconds, the core and/or core plus one or more additional core orcover layers is removed from the mold and either allowed to cool atambient or reduced temperatures or is placed in a cooling fluid such aswater, ice water, dry ice in a solvent, or the like.

When compression molding is used to form a center, the composition isfirst formed into a preform or slug of material, typically in acylindrical or roughly spherical shape at a weight slightly greater thanthe desired weight of the molded core. Prior to this step, thecomposition may be first extruded or otherwise melted and forced througha die after which it is cut into a cylindrical preform. It is thatpreform that is then placed into a compression mold cavity andcompressed at a mold temperature of from 150° F. to 400° F., preferablyfrom 250° F. to 350° F., and more preferably from 260° F. to 295° F.When compression molding a core or cover layer of an HNP composition, ahalf-shell is first formed via injection molding and then a corecomprising one or more layers is enclosed within two half shells andthen compression molded in a similar manner to the process previouslydescribed.

Reaction injection molding processes are further disclosed, for example,in U.S. Pat. Nos. 6,083,119, 7,338,391, 7,282,169, 7,281,997 and U.S.Patent Application Publication No. 2006/0247073, the entire disclosuresof which are hereby incorporated herein by reference.

In a particular aspect of this embodiment, the golf ball has one or moreof the following properties:

-   -   (a) a center having a diameter within a range having a lower        limit of 0.250 or 0.500 or 0.600 or 0.750 or 0.800 or 1.000 or        1.100 or 1.200 inches and an upper limit of 1.300 or 1.350 or        1.400 or 1.500 or 1.510 or 1.530 or 1.550 or 1.570 or 1.580 or        1.600 inches;    -   (b) an intermediate core layer having a thickness within a range        having a lower limit of 0.020 or 0.025 or 0.032 or 0.050 or        0.075 or 0.100 or 0.125 inches and an upper limit of 0.150 or        0.175 or 0.200 or 0.220 or 0.250 or 0.280 or 0.300 inches;    -   (c) an outer core layer having a thickness within a range having        a lower limit of 0.010 or 0.020 or 0.025 or 0.030 or 0.032        inches and an upper limit of 0.070 or 0.080 or 0.100 or 0.150 or        0.310 or 0.440 or 0.560 inches;    -   (d) an intermediate core layer and an outer core layer having a        combined thickness within a range having a lower limit of 0.040        inches and an upper limit of 0.560 or 0.800 inches;    -   (e) an outer core layer having a thickness such that a golf ball        subassembly including the center, intermediate core layer, and        core layer has an outer diameter within a range having a lower        limit of 1.000 or 1.300 or 1.400 or 1.450 or 1.500 or 1.510 or        1.530 or 1.550 inches and an upper limit of 1.560 or 1.570 or        1.580 or 1.590 or 1.600 or 1.620 or 1.640 inches;    -   (f) a center having a surface hardness of 65 Shore C or greater,        or 70 Shore C or greater, or a surface hardness within a range        having a lower limit of 55 or 60 or 65 or 70 or 75 Shore C and        an upper limit of 80 or 85 Shore C;    -   (g) a center having a center hardness (H) within a range having        a lower limit of 20 or 25 or 30 or 35 or 45 or 50 or 55 Shore C        and an upper limit of 60 or 65 or 70 or 75 or 90 Shore C; an        outer core layer having a surface hardness (S) within a range        having a lower limit of 20 or 25 or 30 or 35 or 45 or 55 Shore C        and an upper limit of 60 or 70 or 75 or 90 Shore C; and        -   (i) H=S;        -   (ii) H<S, and the difference between H and S is from −15 to            40, preferably from −15 to 22, more preferably from −10 to            15, and even more preferably from −5 to 10; or        -   (iii) S<H, and the difference between H and S is from −15 to            40, preferably from −15 to 22, more preferably from −10 to            15, and even more preferably from −5 to 10;    -   (h) an intermediate layer having a surface hardness (I) that is        greater than both the center hardness of the center (H) and the        surface hardness of the outer core layer (S); I is preferably 40        Shore C or greater or within a range having an lower limit of 40        or 45 or 50 or 85 Shore C and an upper limit of 90 or 93 or 95        Shore C; the Shore D range for I is preferably from 40 to 80,        more preferably from 50 to 70;    -   (i) each core layer having a specific gravity of from 0.50 g/cc        to 5.00 g/cc; preferably from 1.05 g/cc to 1.25 g/cc; more        preferably from 1.10 g/cc to 1.18 g/cc;    -   (j) a center having a surface hardness greater than or equal to        the center hardness of the center;    -   (k) a center having a positive hardness gradient wherein the        surface hardness of the center is at least 10 Shore C units        greater than the center hardness of the center;    -   (l) an outer core layer having a surface hardness greater than        or equal to the surface hardness and center hardness of the        center;    -   (m) a center having a compression of 40 or less;    -   (n) a center having a compression of from 20 to 40; and    -   (o) a golf ball subassembly including the center and the        intermediate core layer has a compression of 30 or greater, or        40 or greater, or 50 or greater, or 60 or greater, or a        compression within a range having a lower limit of 30 or 40 or        50 or 60 and an upper limit of 65 or 75 or 85 or 95 or 105.

In another embodiment, the present invention is directed to a golf ballcomprising a center, an outer core layer, an intermediate core layerdisposed between the center and the outer core layer, and one or morecover layers, wherein the golf ball has one or more of the followingproperties:

-   -   (a) a center having a diameter within a range having a lower        limit of 0.100 or 0.125 or 0.250 inches and an upper limit of        0.375 or 0.500 or 0.750 or 1.000 inches;    -   (b) an intermediate core layer having a thickness within a range        having a lower limit of 0.050 or 0.075 or 0.100 or 0.125 or        0.150 or 0.200 inches and an upper limit of 0.300 or 0.350 or        0.400 or 0.500 inches;    -   (c) an outer core layer having a thickness within a range having        a lower limit of 0.010 or 0.020 or 0.025 or 0.030 or 0.032        inches and an upper limit of 0.070 or 0.080 or 0.100 or 0.150 or        0.310 or 0.440 or 0.560 inches;    -   (d) an outer core layer having a thickness such that a golf ball        subassembly including the center, intermediate core layer, and        core layer has an outer diameter within a range having a lower        limit of 1.000 or 1.300 or 1.400 or 1.450 or 1.500 or 1.510 or        1.530 or 1.550 inches and an upper limit of 1.560 or 1.570 or        1.580 or 1.590 or 1.600 or 1.620 or 1.640 or 1.660 inches;    -   (e) a center having a surface hardness of 65 Shore C or greater,        or 70 Shore C or greater, or greater than 70 Shore C, or 80        Shore C or greater, or a surface hardness within a range having        a lower limit of 70 or 75 or 80 Shore C and an upper limit of 90        or 95 Shore C;    -   (f) an outer core layer having a surface hardness less than or        equal to the surface hardness of the center;    -   (g) an outer core having a surface hardness of 65 Shore C or        greater, or 70 Shore C or greater, or greater than 70 Shore C,        or 80 Shore C or greater, or 85 Shore C or greater;    -   (h) an intermediate core layer having a surface hardness that is        less than both the surface hardness of the center and the        surface hardness of the outer core layer;    -   (i) an intermediate core layer having a surface hardness of less        than 80 Shore C, or less than 70 Shore C, or less than 60 Shore        C;    -   (j) a center specific gravity less than or equal to or        substantially the same as (i.e., within 0.1 g/cc) the outer core        layer specific gravity;    -   (j) a center specific gravity within a range having a lower        limit of 0.50 or 0.90 or 1.05 or 1.13 g/cc and an upper limit of        1.15 or 1.18 or 1.20 g/cc;    -   (k) an outer core layer specific gravity of 1.00 g/cc or        greater, or 1.05 g/cc or greater, or 1.10 g/cc or greater;    -   (l) an intermediate core layer specific gravity of 1.00 g/cc or        greater, or 1.05 g/cc or greater, or 1.10 g/cc or greater;    -   (m) an intermediate core layer specific gravity substantially        the same as (i.e., within 0.1 g/cc) the outer core layer        specific gravity;    -   (n) a center having a surface hardness greater than or equal to        the center hardness of the center;    -   (o) a center having a positive hardness gradient wherein the        surface hardness of the center is at least 10 Shore C units        greater than the center hardness of the center;    -   (p) a center having a compression of 40 or less;    -   (q) a center having a compression of from 20 to 40; and    -   (r) a golf ball subassembly including the center and the        intermediate core layer has a compression of 30 or greater, or        40 or greater, or 50 or greater, or 60 or greater, or a        compression within a range having a lower limit of 30 or 40 or        50 or 60 or 65 and an upper limit of 70 or 75 or 85 or 90 or 95        or 105.

In another embodiment, the present invention is directed to a golf ballcomprising a center, an outer core layer, and one or more cover layers.In a particular aspect of this embodiment, the golf ball has one or moreof the following properties:

-   -   (a) a center having a diameter within a range having a lower        limit of 0.500 or 0.750 or 1.000 or 1.100 or 1.200 inches and an        upper limit of 1.300 or 1.350 or 1.400 or 1.550 or 1.570 or        1.580 inches;    -   (b) a center having a diameter within a range having a lower        limit of 0.750 or 0.850 or 0.875 inches and an upper limit of        1.125 or 1.150 or 1.190 inches;    -   (c) an outer core layer enclosing the center such that the        dual-layer core has an overall diameter within a range having a        lower limit of 1.400 or 1.500 or 1.510 or 1.520 or 1.525 inches        and an upper limit of 1.540 or 1.550 or 1.555 or 1.560 or 1.590        inches, or an outer core layer having a thickness within a range        having a lower limit of 0.020 or 0.025 or 0.032 inches and an        upper limit of 0.310 or 0.440 or 0.560 inches;    -   (d) a center having a center hardness of 50 Shore C or greater,        or 55 Shore C or greater, or 60 Shore C or greater, or a center        hardness within a range having a lower limit of 50 or 55 or 60        Shore C and an upper limit of 65 or 70 or 80 Shore C;    -   (e) a center having a surface hardness of 65 Shore C or greater,        or 70 Shore C or greater, or a surface hardness within a range        having a lower limit of 55 or 60 or 65 or 70 or 75 Shore C and        an upper limit of 80 or 85 Shore C;    -   (f) an outer core layer having a surface hardness of 75 Shore C        or greater, or 80 Shore C or greater, or greater than 80 Shore        C, or 85 Shore C or greater, or greater than 85 Shore C, or 87        Shore C or greater, or greater than 87 Shore C, or 89 Shore C or        greater, or greater than 89 Shore C, or 90 Shore C or greater,        or greater than 90 Shore C, or a surface hardness within a range        having a lower limit of 75 or 80 or 85 Shore C and an upper        limit of 95 Shore C;    -   (g) a center having a surface hardness greater than or equal to        the center hardness of the center;    -   (h) a center having a positive hardness gradient wherein the        surface hardness of the center is at least 10 Shore C units        greater than the center hardness of the center;    -   (i) an outer core layer having a surface hardness greater than        or equal to the surface hardness and center hardness of the        center;    -   (j) a core having a positive hardness gradient wherein the        surface hardness of the outer core layer is at least 20 Shore C        units greater, or at least 25 Shore C units greater, or at least        30 Shore C units greater, than the center hardness of the        center;    -   (k) a center having a compression of 40 or less; and    -   (l) a center having a compression of from 20 to 40.

The weight distribution of cores disclosed herein can be varied toachieve certain desired parameters, such as spin rate, compression, andinitial velocity.

Golf ball cores of the present invention typically have an overall corecompression of less than 100, or a compression of 87 or less, or anoverall core compression within a range having a lower limit of 20 or 50or 60 or 65 or 70 or 75 and an upper limit of 80 or 85 or 90 or 100 or110 or 120, or an overall core compression of about 80. Compression isan important factor in golf ball design. For example, the compression ofthe core can affect the ball's spin rate off the driver and the feel. Asdisclosed in Jeff Dalton's Compression by Any Other Name, Science andGolf IV, Proceedings of the World Scientific Congress of Golf (EricThain ed., Routledge, 2002) (“J. Dalton”), several different methods canbe used to measure compression, including Atti compression, Riehlecompression, load/deflection measurements at a variety of fixed loadsand offsets, and effective modulus. For purposes of the presentinvention, “compression” refers to Atti compression and is measuredaccording to a known procedure, using an Atti compression test device,wherein a piston is used to compress a ball against a spring. The travelof the piston is fixed and the deflection of the spring is measured. Themeasurement of the deflection of the spring does not begin with itscontact with the ball; rather, there is an offset of approximately thefirst 1.25 mm (0.05 inches) of the spring's deflection. Very lowstiffness cores will not cause the spring to deflect by more than 1.25mm and therefore have a zero compression measurement. The Atticompression tester is designed to measure objects having a diameter of42.7 mm (1.68 inches); thus, smaller objects, such as golf ball cores,must be shimmed to a total height of 42.7 mm to obtain an accuratereading. Conversion from Atti compression to Riehle (cores), Riehle(balls), 100 kg deflection, 130-10 kg deflection or effective moduluscan be carried out according to the formulas given in J. Dalton.

Golf ball cores of the present invention typically have a coefficient ofrestitution (“COR”) at 125 ft/s of at least 0.75, preferably at least0.78, and more preferably at least 0.79. COR, as used herein, isdetermined according to a known procedure wherein a golf ball or golfball subassembly (e.g., a golf ball core) is fired from an air cannon ata given velocity (125 ft/s for purposes of the present invention).Ballistic light screens are located between the air cannon and the steelplate to measure ball velocity. As the ball travels toward the steelplate, it activates each light screen, and the time at each light screenis measured. This provides an incoming transit time period proportionalto the ball's incoming velocity. The ball impacts the steel plate andrebounds through the light screens, which again measure the time periodrequired to transit between the light screens. This provides an outgoingtransit time period proportional to the ball's outgoing velocity. COR isthen calculated as the ratio of the outgoing transit time period to theincoming transit time period, COR=T_(out)/T_(in).

Cores of the present invention are enclosed with a cover, which may be asingle-, dual-, or multi-layer cover. The cover may for example have asingle layer with a surface hardness of 65 Shore D or less, or 60 ShoreD or less, or 45 Shore D or less, or 40 Shore D or less, or from 25Shore D to 40 Shore D, or from 30 Shore D to 40 Shore D and a thicknesswithin a range having a lower limit of 0.010 or 0.015 or 0.020 or 0.025or 0.030 or 0.055 or 0.060 inches and an upper limit of 0.065 or 0.080or 0.090 or 0.100 or 0.110 or 0.120 or 0.140 inches. The flexuralmodulus of the cover, as measured by ASTM D6272-98 Procedure B, ispreferably 500 psi or greater, or from 500 psi to 150,000 psi.

In another particular embodiment, the cover is a two-layer coverconsisting of an inner cover layer and an outer cover layer. The innercover layer may for example have has a surface hardness of 60 Shore D orgreater, or 65 Shore D or greater, or a surface hardness within a rangehaving a lower limit of 30 or 40 or 55 or 60 or 65 Shore D and an upperlimit of 66 or 68 or 70 or 75 Shore D, and a thickness within a rangehaving a lower limit of 0.010 or 0.015 or 0.020 or 0.030 inches and anupper limit of 0.035 or 0.040 or 0.045 or 0.050 or 0.055 or 0.075 or0.080 or 0.100 or 0.110 or 0.120 inches. The inner cover layercomposition preferably has a material hardness of 95 Shore C or less, orless than 95 Shore C, or 92 Shore C or less, or 90 Shore C or less, orhas a material hardness within a range having a lower limit of 70 or 75or 80 or 84 or 85 Shore C and an upper limit of 90 or 92 or 95 Shore C.The outer cover layer material can be thermosetting, or thermoplastic.The outer cover layer composition preferably has a material hardness of85 Shore C or less, or 45 Shore D or less, or 40 Shore D or less, orfrom 25 Shore D to 40 Shore D, or from 30 Shore D to 40 Shore D. Theouter cover layer preferably has a surface hardness within a rangehaving a lower limit of 20 or 30 or 35 or 40 Shore D and an upper limitof 52 or 58 or 60 or 65 or 70 or 72 or 75 Shore D. The outer cover layerpreferably has a thickness within a range having a lower limit of 0.010or 0.015 or 0.025 inches and an upper limit of 0.035 or 0.040 or 0.045or 0.050 or 0.055 or 0.075 or 0.080 or 0.115 inches. The two-layer coverpreferably has an overall thickness within a range having a lower limitof 0.010 or 0.015 or 0.020 or 0.025 or 0.030 or 0.055 or 0.060 inchesand an upper limit of 0.065 or 0.075 or 0.080 or 0.090 or 0.100 or 0.110or 0.120 or 0.140 inches.

In another particular embodiment, the cover is a dual-layer covercomprising an inner cover layer and an outer cover layer. In aparticular aspect of this embodiment, the surface hardness of the outercore layer is greater than the material hardness of the inner coverlayer. In another particular aspect of this embodiment, the surfacehardness of the outer core layer is greater than both the inner coverlayer and the outer cover layer. The inner cover layer preferably has amaterial hardness of 95 Shore C or less, or less than 95 Shore C, or 92Shore C or less, or 90 Shore C or less, or has a material hardnesswithin a range having a lower limit of 70 or 75 or 80 or 84 or 85 ShoreC and an upper limit of 90 or 92 or 95 Shore C. The thickness of theinner cover layer is preferably within a range having a lower limit of0.010 or 0.015 or 0.020 or 0.030 inches and an upper limit of 0.035 or0.045 or 0.080 or 0.120 inches. The outer cover layer preferably has amaterial hardness of 85 Shore C or less. The thickness of the outercover layer is preferably within a range having a lower limit of 0.010or 0.015 or 0.025 inches and an upper limit of 0.035 or 0.040 or 0.055or 0.080 inches.

A moisture vapor barrier layer is optionally employed between the coreand the cover. Moisture vapor barrier layers are further disclosed, forexample, in U.S. Pat. Nos. 6,632,147, 6,932,720, 7,004,854, and7,182,702, the entire disclosures of which are hereby incorporatedherein by reference.

Golf balls of the present invention typically have a compression of 120or less, or a compression within a range having a lower limit of 40 or50 or 60 or 65 or 75 or 80 or 90 and an upper limit of 95 or 100 or 105or 110 or 115 or 120. Golf balls of the present invention typically havea COR at 125 ft/s of at least 0.70, preferably at least 0.75, morepreferably at least 0.78, and even more preferably at least 0.79.

Golf balls of the present invention will typically have dimple coverageof 60% or greater, preferably 65% or greater, and more preferably 75% orgreater. The United States Golf Association specifications limit theminimum size of a competition golf ball to 1.680 inches. There is nospecification as to the maximum diameter, and golf balls of any size canbe used for recreational play. Golf balls of the present invention canhave an overall diameter of any size. The preferred diameter of thepresent golf balls is from 1.680 inches to 1.800 inches. Morepreferably, the present golf balls have an overall diameter of from1.680 inches to 1.760 inches, and even more preferably from 1.680 inchesto 1.740 inches.

Golf balls of the present invention preferably have a moment of inertia(“MOI”) of 70-95 g·cm², preferably 75-93 g·cm², and more preferably76-90 g·cm². For low MOI embodiments, the golf ball preferably has anMOI of 85 g·cm² or less, or 83 g·cm² or less. For high MOI embodiment,the golf ball preferably has an MOI of 86 g·cm² or greater, or 87 g·cm²or greater. MOI is measured on a model MOI-005-104 Moment of InertiaInstrument manufactured by Inertia Dynamics of Collinsville, Conn. Theinstrument is connected to a PC for communication via a COMM port and isdriven by MOI Instrument Software version #1.2.

Thermoplastic layers herein may be treated in such a manner as to createa positive or negative hardness gradient. In golf ball layers of thepresent invention wherein a thermosetting rubber is used,gradient-producing processes and/or gradient-producing rubberformulation may be employed. Gradient-producing processes andformulations are disclosed more fully, for example, in U.S. patentapplication Ser. No. 12/048,665, filed on Mar. 14, 2008; Ser. No.11/829,461, filed on Jul. 27, 2007; Ser. No. 11/772,903, filed Jul. 3,2007; Ser. No. 11/832,163, filed Aug. 1, 2007; Ser. No. 11/832,197,filed on Aug. 1, 2007; the entire disclosure of each of these referencesis hereby incorporated herein by reference.

What is claimed is:
 1. A golf ball having at least one layer comprisinga highly neutralized acid polymer composition consisting of a mixtureof: at least one ethylene acid copolymer; a sufficient amount of cationsource to neutralize greater than about 100% of all acid groups present;and a highly diverse mixture of at least 20 organic acids exhibiting thechromatogram of FIG.
 1. 2. The golf ball of claim 1, wherein all organicacids of the highly diverse mixture are carboxylic acids.
 3. The golfball of claim 1, wherein at least 90% of the organic acids of the highlydiverse mixture are fatty acids.
 4. The golf ball of claim 1, wherein atleast two organic acids of the highly diverse mixture have differentcarbon chain lengths.
 5. The golf ball of claim 4, wherein the carbonchain lengths differ by at least two carbon atoms.
 6. The golf ball ofclaim 1, wherein at least three organic acids of the highly diversemixture have different carbon chain lengths.
 7. The golf ball of claim6, wherein the carbon chain lengths differ by at least two carbon atoms.8. The golf ball of claim 1, wherein no single organic acid is presentin the highly diverse mixture in a concentration greater than 40%. 9.The golf ball of claim 1, wherein the highly diverse mixture containssaturated organic acids and unsaturated organic acids.
 10. The golfballs of claim 9, wherein one organic acid has a carbon chain having adifferent number of carbon-carbon double bonds than a carbon chain of atleast one other organic acid.
 11. The golf ball of claim 1, wherein afirst organic acid has a first carbon chain and a second organic acidhas a second carbon chain having the same number of carbon-carbon doublebonds as the first carbon chain; and wherein at least one carbon-carbondouble bond position on the first carbon chain is not a carbon-carbondouble bond position on the second carbon chain.
 12. The golf ball ofclaim 10, wherein at least one organic acid has a cis-type carbon-carbondouble bond configuration and at least one other organic acid has atrans-type carbon-carbon double bond configuration.
 13. The golf ball ofclaim 1, wherein at least one organic acid has a carbon chain that isbranched differently than a carbon chain of at least one other organicacid.
 14. The golf ball of claim 13, wherein one organic acid has acarbon chain having a different number of branches than a carbon chainof at least one other organic acid.
 15. The golf ball of claim 1,wherein a first organic acid has a first carbon chain and a secondorganic acid has a second carbon chain having the same number ofbranches as the first carbon chain; and wherein at least one branchposition on the first carbon chain is not a branch position on thesecond carbon chain.
 16. The golf ball of claim 1, wherein at least twoorganic acids have different functional groups.
 17. The golf ball ofclaim 16, wherein one functional group is carboxylic acid.
 18. The golfball of claim 1, wherein the highly diverse mixture comprises at leastone aliphatic organic acid and at least one aromatic organic acid. 19.The golf ball of claim 1, wherein the highly diverse mixture containsorganic acids having two or more different characteristics.
 20. The golfball of claim 1, wherein the highly diverse mixture contains organicacids having three or more different characteristics.
 21. The golf ballof claim 1, wherein the highly diverse mixture contains organic acidshaving four or more different characteristics.
 22. The golf ball ofclaim 1, wherein the highly diverse mixture contains organic acidshaving five or more different characteristics.
 23. A golf ball having atleast one layer comprising a highly neutralized acid polymer compositionconsisting of a mixture of: at least one ethylene acid copolymer; asufficient amount of cation source to neutralize greater than about 100%of all acid groups present; and a highly diverse mixture of at least 14organic acids exhibiting the chromatogram of FIG.
 2. 24. A golf ballhaving at least one layer comprising a highly neutralized acid polymercomposition consisting of a mixture of: at least one ethylene acidcopolymer; a sufficient amount of cation source to neutralize greaterthan about 100% of all acid groups present; and a highly diverse mixtureof at least 15 organic acids exhibiting the chromatogram of FIG. 3.